Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers

Science.gov (United States)

Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

Mechanical Properties of Weakly Segregated Block Copolymers. 3. Influence of Strain Rate and Temperature on Tensile Properties of Poly(styrene-b-butyl methacrylate) Diblock Copolymers with Different Morphologies

NARCIS (Netherlands)

Weidisch, R.; Stamm, M.; Michler, G.H.; Fischer, H.R.; Jérôme, R.

1999-01-01

Poly(styrene-b-butyl methacrylate) diblock copolymers, PS-6-PBMA, with different morphologies are investigated with respect to the influence of strain rate and temperature on tensile properties. In the first part the mechanical properties of bicontinuous and perforated lamellar structure are

Crystallization in diblock copolymer thin films at different degrees of supercooling

DEFF Research Database (Denmark)

Darko, C.; Botiz, I.; Reiter, G.

2009-01-01

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 interme...

Barriers to defect melting in chemo-epitaxial directed self-assembly of lamellar-forming diblock copolymer/homopolymer blends

Science.gov (United States)

Izumi, Kenichi; Kim, Bongkeun; Laachi, Nabil; Delaney, Kris T.; Carilli, Michael; Fredrickson, Glenn H.

2015-03-01

We investigate energy barriers and minimum energy paths (MEPs) for transitions from dislocation-pair defects to perfect lamellae in self-assembly of AB-diblock copolymer plus A- or B-homopolymer blends using self-consistent field theory (SCFT) and the numerical string method. For neutral substrates, all minimum energy paths discovered by the string method show two successive energy barriers. The two-barrier qualitative nature of the MEPs appears not to depend on the presence or absence of small amounts of homopolymer. For the first energy barrier, the barrier height shows pronounced increase with addition of A-homopolymer due to localization of A-homopolymer on the T-junction core of the dislocation. For chemo-epitaxially patterned substrates (stripes of A-attractive substrate alternating with neutral substrate), the presence of A-attractive stripes helps draw the system towards a perfect lamellar configuration, and energy barriers along the MEP are reduced, in some cases disappearing entirely. Our findings provide guidance on how the presence of homopolymer and chemo-epitaxial prepatterns affect the stability of defective morphologies.

The color tuning of PS-b-P2VP lamellar films with changing the alkyl chain length of 1-iodoalkanes.

Science.gov (United States)

Shin, Sung-Eui; Kim, Su-Young; Shin, Dong-Myung

2011-05-01

Photonic crystals with tunability in the visible or near-infrared region have drawn increasing attention for controlling and processing light for the active components of future display. We prepared polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) lamellar films which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 57 kg/mol-b-57 kg/mol. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic moiety of PS-b-P2VP, are obtained by exposing the spin coated film under chloroform vapor. The band gaps of the lamellar films interestingly varied after immersion into the quaternizing solvents containing 5 wt% of iodomethane, iodoethane, 1-iodobutane, 1-iodopentane, 1-iodohexane and 1-iodooctane solubilized in n-hexane. The iodoalkanes reacted with pyridine groups in PS-b-P2VP and generated the alkyl pyridinium salts readily. The degree of quaternization, alkyl chain length of iodoalkane and the salt water concentration affects the spacing of layer structure of PS-b-P2VP. The iodomethane and iodohexane produced similar band gaps and salt concentration dependence. These results are very much dependent on the hydrophobic-hydrophilic characters of PS-b-P2VP lamellar surface.

Small-angle neutron scattering investigation of the chain conformation of lamellar polystyrene/isoprene phase in solid state

International Nuclear Information System (INIS)

Constantinescu, L.M.

1994-01-01

Small-angle neutron scattering has been used in the study of chain conformation of lamellar styrene/isoprene block copolymers oriented in large single crystals. The radius of gyration of deuterated polystyrene chains around the normal to the interface has been measured. By comparing this direct evolution of the lateral dimension of the chains with the average chain separation given by the molecular area (the surface available at the interface for each covalent bond linking the blocks together) we characterized the transverse interpenetration degree of the chains. The polystyrene chains are displayed in simple strata own micro-domains, without an important interpenetration. (Author) 9 Figs., 2 Tabs., 25 Refs

Merging Bottom-Up with Top-Down: Continuous Lamellar Networks and Block Copolymer Lithography

Science.gov (United States)

Campbell, Ian Patrick

Block copolymer lithography is an emerging nanopatterning technology with capabilities that may complement and eventually replace those provided by existing optical lithography techniques. This bottom-up process relies on the parallel self-assembly of macromolecules composed of covalently linked, chemically distinct blocks to generate periodic nanostructures. Among the myriad potential morphologies, lamellar structures formed by diblock copolymers with symmetric volume fractions have attracted the most interest as a patterning tool. When confined to thin films and directed to assemble with interfaces perpendicular to the substrate, two-dimensional domains are formed between the free surface and the substrate, and selective removal of a single block creates a nanostructured polymeric template. The substrate exposed between the polymeric features can subsequently be modified through standard top-down microfabrication processes to generate novel nanostructured materials. Despite tremendous progress in our understanding of block copolymer self-assembly, continuous two-dimensional materials have not yet been fabricated via this robust technique, which may enable nanostructured material combinations that cannot be fabricated through bottom-up methods. This thesis aims to study the effects of block copolymer composition and processing on the lamellar network morphology of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) and utilize this knowledge to fabricate continuous two-dimensional materials through top-down methods. First, block copolymer composition was varied through homopolymer blending to explore the physical phenomena surrounding lamellar network continuity. After establishing a framework for tuning the continuity, the effects of various processing parameters were explored to engineer the network connectivity via defect annihilation processes. Precisely controlling the connectivity and continuity of lamellar networks through defect engineering and

Ultrasonic degradation of butadiene, styrene and their copolymers.

Science.gov (United States)

Sathiskumar, P S; Madras, Giridhar

2012-05-01

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

Controlled supramolecular assembly of micelle-like gold nanoparticles in PS-b-P2VP diblock copolymers via hydrogen bonding.

Science.gov (United States)

Jang, Se Gyu; Kramer, Edward J; Hawker, Craig J

2011-10-26

We report a facile strategy to synthesize amphiphilic gold (Au) nanoparticles functionalized with a multilayer, micelle-like structure consisting of a Au core, an inner hydroxylated polyisoprene (PIOH) layer, and an outer polystyrene shell (PS). Careful control of enthalpic interactions via a systematic variation of structural parameters, such as number of hydroxyl groups per ligand (N(OH)) and styrene repeating units (N(PS)) as well as areal chain density of ligands on the Au-core surface (Σ), enables precise control of the spatial distribution of these nanoparticles. This control was demonstrated in a lamellae-forming poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) diblock copolymer matrix, where the favorable hydrogen-bonding interaction between hydroxyl groups in the PIOH inner shell and P2VP chains in the PS-b-P2VP diblock copolymer matrix, driving the nanoparticles to be segregated in P2VP domains, could be counter balanced by the enthalphic penalty of mixing of the PS outer brush with the P2VP domains. By varying N(OH), N(PS), and Σ, the nanoparticles could be positioned in the PS or P2VP domains or at the PS/P2VP interface. In addition, the effect of additives interfering with the hydrogen-bond formation between hydroxyl groups on Au nanoparticles and P2VP chains in a diblock copolymer matrix was investigated, and an interesting pea-pod-like segregation of Au nanoparticles in PS domains was observed.

Stepwise swelling of a thin film of lamellae-forming poly(styrene-b- butadiene) in cyclohexane vapor

KAUST Repository

Di, Zhenyu; Posselt, Dorthe; Smilgies, Detlef Matthias; Li, Ruipeng; Rauscher, Markus; Potemkin, Igor I.; Papadakis, Christine M.

2012-01-01

We investigated the swelling of a thin film of lamellae-forming poly(styrene-b-butadiene) in cyclohexane vapor. The vapor pressure and thus the degree of swelling of the film are increased in a stepwise manner using a custom-built sample cell. The resulting structural changes during and after each step were followed in situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). During the first step, the lamellar thickness increases strongly, before it decreases again. At the same time, the full width at half-maximum (FWHM) of the diffuse Bragg reflection along the film normal has a sharp maximum. These observations point to the formation of new lamellae. During the subsequent swelling steps, the lamellar thickness overshoots only weakly. The behavior thus resembles qualitatively our previous results on a similar thin film during swelling in saturated vapor of cyclohexane; however, it deviates from earlier theoretical predictions. We propose a theory that is quantitatively correct for the description of the dependence of the lamellar thickness on the polymer volume fraction in the late stage of the swelling steps. © 2012 American Chemical Society.

Stepwise swelling of a thin film of lamellae-forming poly(styrene-b- butadiene) in cyclohexane vapor

KAUST Repository

Di, Zhenyu

2012-06-26

We investigated the swelling of a thin film of lamellae-forming poly(styrene-b-butadiene) in cyclohexane vapor. The vapor pressure and thus the degree of swelling of the film are increased in a stepwise manner using a custom-built sample cell. The resulting structural changes during and after each step were followed in situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). During the first step, the lamellar thickness increases strongly, before it decreases again. At the same time, the full width at half-maximum (FWHM) of the diffuse Bragg reflection along the film normal has a sharp maximum. These observations point to the formation of new lamellae. During the subsequent swelling steps, the lamellar thickness overshoots only weakly. The behavior thus resembles qualitatively our previous results on a similar thin film during swelling in saturated vapor of cyclohexane; however, it deviates from earlier theoretical predictions. We propose a theory that is quantitatively correct for the description of the dependence of the lamellar thickness on the polymer volume fraction in the late stage of the swelling steps. © 2012 American Chemical Society.

Adsorption and Aqueous Lubricating Properties of Charged and Neutral Amphiphilic Diblock Copolymers at a Compliant, Hydrophobic Interface

DEFF Research Database (Denmark)

Røn, Troels; Javakhishvili, Irakli; Jankova Atanasova, Katja

2013-01-01

We have investigated the adsorption and lubricating properties of neutral and charged amphiphilic diblock copolymers at a hydrophobic polydimethylsiloxane (PDMS) interface in an aqueous environment. The diblock copolymers consist of a hydrophilic block of either neutral poly(ethylene glycol) (PEG......) or negatively charged poly(acrylic acid) (PAA) and of a hydrophobic block of polystyrene (PS) or poly(2-methoxyethyl acrylate) (PMEA), thus generating PEG-b-X or PAA-b-X, where X block is either PS or PMEA. The molecular weight ratios were roughly 1:1 with each block ca. 5 kDa. Comparing the neutral PEG...... effective adsorption only when PMEA was employed as the anchoring block. For PAA-b-PS, the poor adsorption properties are chiefly attributed to micellization due to the high interfacial tension between the PS core and water. The poor lubricating properties of PAA-b-PS diblock copolymer for a PDMS...

Preparation of polystyrene-poly(ethylene glycol) diblock copolymer by "living" free radical polymerization

DEFF Research Database (Denmark)

Chen, Xianyi; Gao, Bo; Kops, Jørgen

1998-01-01

terminated with a TEMPO unit (MPEG-TEMPO), which was further used to prepare the diblock copolymer PS-b-PEG by 'living' free radical polymerisation of styrene. The product was purified and identified by H-1 n.m.r. and GPC. However, large amounts of homopolystyrene was also formed by simultaneous thermal...

Lamellar Microdomains of Block-Copolymer-Based Ionic Supramolecules Exhibiting a Hierarchical Self-Assembly

DEFF Research Database (Denmark)

Ayoubi, Mehran Asad; Almdal, Kristoffer; Zhu, Kaizheng

2014-01-01

(Cn; n = 8, 12, and 16) trimethylammonium counterions (i.e., side chains) at various ion (pair) fractions X [i.e., counterion/side-chain grafting density; X = number of alkyl counterions (i.e., side chains) per acidic group of the parent PMAA block] these L-b-AC ionic supramolecules exhibit...... a spherical-in-lamellar hierarchical self-assembly. For these systems, (1) the effective Flory-Huggins interaction parameter between L- and AC-blocks chi'(Cn/x) was extracted, and (2) analysis of the lamellar microdomains showed that when there is an increase in X, alkyl counterion (i.e., side chain) length l......Based on a parent diblock copolymer of poly(styrene)-b-poly(methacrylic acid), PS-b-PMAA, linear-b-amphiphilic comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] are synthesized in which the poly(methacrylate) backbone of the ionic supramolecular AC-block is neutralized by alkyl...

Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

KAUST Repository

Musteata, Valentina-Elena; Sutisna, Burhannudin; Polymeropoulos, Georgios; Avgeropoulos, Apostolos; Meneau, Florian; Peinemann, Klaus-Viktor; Hadjichristidis, Nikolaos; Nunes, Suzana Pereira

2017-01-01

Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

KAUST Repository

Musteata, Valentina-Elena

2017-11-08

Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

(Quasi-) 2D aggregation of polystyrene-b-dextran at the air-water interface.

Science.gov (United States)

Bosker, Wouter T E; Cohen Stuart, Martien A; Norde, Willem

2013-02-26

Polystyrene-b-dextran (PS-b-Dextran) copolymers can be used to prepare dextran brushes at solid surfaces, applying Langmuir-Blodgett deposition. When recording the interfacial pressure versus area isotherms of a PS-b-Dextran monolayer, time-dependent hysteresis was observed upon compression and expansion. We argue that this is due to (quasi-) 2D aggregation of the copolymer at the air-water surface, with three contributions. First, at large area per molecule, a zero surface pressure is measured; we ascribe this to self-assembly of block copolymers into surface micelles. At intermediate area we identify a second regime ("desorption regime") where aggregation into large patches occurs due to van der Waals attraction between PS blocks. At high surface pressure ("brush regime") we observe hysteretic behavior attributed to H-bonding between dextran chains. When compared to hysteresis of other amphiphilic diblock copolymers (also containing PS, e.g., polystyrene-b-poly(ethylene oxide)) a general criterion can be formulated concerning the extent of hysteresis: when the hydrophobic (PS) block is of equal size as (or bigger than) the hydrophilic block, the hysteresis is maximal. The (quasi-) 2D aggregation of PS-b-Dextran has significant implications for the preparation of dextran brushes at solid surfaces using Langmuir-Blodgett deposition. For each grafting density the monolayer needs to relax, up to several hours, prior to transfer.

Hydrophilic nanoporous polystyrenes and 1,2-polybutadienes

DEFF Research Database (Denmark)

Guo, Fengxiao; Jankova Atanasova, Katja; Vigild, Martin Etchells

2008-01-01

Nanoporous polymers from ordered block copolymers having hydrophilic cavity surfaces were successfully prepared by two methodologies: ' 1. Nanoporous polystyrenes fromPtBA-b-PS diblock or PDMS-b-PtBA-b-PS triblock copolymer precursors by atom transfer radical polymerization (ATRP), or combination...... of living anionic polymerization~ and ATRP r~spectively. The one, PtBA block, can be modified to the hydrophilic PAA, where the dther, polydimethysiloxane (PDMS) block, can be fully degraded. Deprotection of the tert-butyl groups in PtBA and the selective etching of PDMS· chains were accomplished...... by applying HF or TFA in one step. Thus both the di- and triblock copolymers after such a treatment resulted. in nanoporous polystyrenes with hexagonal cavities of different nanosizes (6-11 nm, Figure 1). 2. Nanoporous I,2-polybutadienes (I,2-PB) by grafting various acrylic monomers onto the pore. surfaces...

Directing self-assembly of gold nanoparticles in diblock copolymer scaffold

Science.gov (United States)

Li, Qifang; He, Jinbo; Glogowski, Elizabeth; Emrick, Todd; Russell, Thomas

2007-03-01

A versatile hierarchical approach for directing self -assembly of gold nanostructures with size 2-3nm in diblock copolymer scaffolds is found. Diblock copolymer polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) is used to form a regular scaffold of highly anisotropic, stripe-like domains, and controlled differential wetting by dichloromethane and thermal annealing guides gold nanoparticles with half hydrophilic ligand to aggregate selectively along the scaffold, producing highly organized metal nanostructures. In as-cast block-copolymer and gold nanoparticles thin films, micelle structure and gold nanoparticles random distribution on scaffold are typically observed. However, samples annealed in dichloromethane exhibit well-defined short-range ordered nanostructure with gold nanoparticles located at the interface of PS and P2VP nanoscale domain. After annealing at 170 C, the gold nanoparticles at interface migrated into the middle of P2VP phase and exhibited long-range ordered hierarchical structures. Synergistic interactions between the gold nanoparticles and the PS-b-P2VP caused an orientation of the microdomains normal to the film surface.

Nanoparticle Encapsulation in Diblock Copolymer/Homopolymer Blend Thin Film Mixtures

Science.gov (United States)

Zhao, Junnan; Chen, Xi; Green, Peter

2014-03-01

We investigated the organization of low concentrations of poly (2-vinylpyridine) (P2VP) grafted gold nanoparticles within a diblock copolymer polystyrene-b-poly (2-vinylpyridine) (PS-b-P2VP)/homopolymer polystyrene (PS) blend thin film. The PS-b-P2VP copolymers formed micelles, composed of inner cores of P2VP block and outer coronae of PS blocks, throughout the homopolymer PS. All nanoparticles were encapsulated within micelle cores and each micelle contained one or no nanoparticle, on average. When the host PS chains are much longer than corona chains, micelles tended to self-organize at the interfaces. Otherwise, they were dispersed throughout the PS host. In comparison to the neat PS-b-P2VP/PS blend, the nanoparticles/PS-b-P2VP/PS system had a higher density of smaller micelles, influenced largely by the number of nanoparticles in the system. The behavior of this system is understood in terms of the maximization of the nanoparticle/micelle core interactions and of the translational entropies of the micelles and the nanoparticles.

Single-molecule tracking studies of flow-induced microdomain alignment in cylinder-forming polystyrene-poly(ethylene oxide) diblock copolymer films.

Science.gov (United States)

Tran-Ba, Khanh-Hoa; Higgins, Daniel A; Ito, Takashi

2014-09-25

Flow-based approaches are promising routes to preparation of aligned block copolymer microdomains within confined spaces. An in-depth characterization of such nanoscale morphologies within macroscopically nonuniform materials under ambient conditions is, however, often challenging. In this study, single-molecule tracking (SMT) methods were employed to probe the flow-induced alignment of cylindrical microdomains (ca. 22 nm in diameter) in polystyrene-poly(ethylene oxide) diblock copolymer (PS-b-PEO) films. Films of micrometer-scale thicknesses were prepared by overlaying a benzene solution droplet on a glass coverslip with a rectangular glass plate, followed by solvent evaporation under a nitrogen atmosphere. The microdomain alignment was quantitatively assessed from SMT data exhibiting the diffusional motions of individual sulforhodamine B fluorescent probes that preferentially partitioned into cylindrical PEO microdomains. Better overall microdomain orientation along the flow direction was observed near the substrate interface in films prepared at a higher flow rate, suggesting that the microdomain alignment was primarily induced by shear flow. The SMT data also revealed the presence of micrometer-scale grains consisting of highly ordered microdomains with coherent orientation. The results of this study provide insights into shear-based preparation of aligned cylindrical microdomains in block copolymer films from solutions within confined spaces.

Directed Self-Assembly of Poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) Triblock Copolymer with Sub-15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template.

Science.gov (United States)

Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Choi, Jaewon; Huang, Caili; Jeong, Gajin; Coughlin, E Bryan; Hsu, Yautzong; Yang, XiaoMin; Lee, Kim Y; Kuo, David S; Xiao, Shuaigang; Russell, Thomas P

2015-08-05

Low molecular weight P2VP-b-PS-b-P2VP triblock copolymer (poly(2-vinlypyridine)-block-polystyrene-block-poly(2-vinylpyridine)] is doped with copper chloride and microphase separated into lamellar line patterns with ultrahigh area density. Salt-doped P2VP-b-PS-b-P2VP triblock copolymer is self-assembled on the top of the nanoimprinted photoresist template, and metallic nanowires with long-range ordering are prepared with platinum-salt infiltration and plasma etching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of integral asymmetric membranes of AB diblock and ABC triblock copolymers by phase inversion.

Science.gov (United States)

Jung, Adina; Filiz, Volkan; Rangou, Sofia; Buhr, Kristian; Merten, Petra; Hahn, Janina; Clodt, Juliana; Abetz, Clarissa; Abetz, Volker

2013-04-12

The formation of integral asymmetric membranes from ABC triblock terpolymers by non-solvent-induced phase separation is shown. They are compared with the AB diblock copolymer precursors. Triblock terpolymers of polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two compositions are investigated. The third block supports the formation of a membrane in a case, where the corresponding diblock copolymer does not form a good membrane. In addition, the hydrophilicity is increased by the third block and due to the hydroxyl group the possibility of post-functionalization is given. The morphologies are imaged by scanning electron microscopy. The influence of the PEO on the membrane properties is analyzed by water flux, retention, and dynamic contact angle measurements. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoscopic multiphase structures and the interfaces of block and graft copolymers in bulk

International Nuclear Information System (INIS)

Matsushita, Yushu

1996-01-01

Microphase-separated structures of copolymers with various architectures and their polymer/polymer interfaces were studied. They are SP diblock, PSP triblock, and SPP graft copolymers, where S and P denote polystyrene and poly(2-vinylpyridine), respectively. Morphological observations were carried out by means of transmission electron microscopy and small-angle X-ray scattering. Chain dimensions of component polymers were measured by small-angle neutron scattering and microphase-separated interfaces were observed by neutron reflectivity measurements using deuterium-labeled samples. It was clarified that morphological phase transitions among thermodynamically equilibrium structures for SP diblock and PSP triblock copolymers occur at almost the same compositions; however, those of SPP graft copolymers tend to occur at higher volume fraction of polystyrene, φ s , than those for block copolymers. As for alternating lamellar structures it turned out to be clear that lamellar domain spacings, D's, were scaled as the 2/3 power of the molecular weight of polymers irrespective of their architectures. S block chains of SP diblock and PSP triblock copolymers in lamellar structures were both confirmed to be deformed toward the direction perpendicular to the lamellar interfaces, but it revealed that their volumes were preserved. Further, S/P interfacial thicknesses of SP and PSP were essentially the same to each other and the values defined as the FWHM of the error functions which express the segment density distributions of the interfaces were determined to be about 4 nm. (author)

Morphological investigation of polydisperse asymmetric block copolymer systems of poly(styrene) and poly(methacrylic acid) in the strong segregation regime

DEFF Research Database (Denmark)

Asad Ayoubi, Mehran; Zhu, Kaizheng; Nyström, Bo

2013-01-01

Samples of compositionally (highly) asymmetric diblock copolymers and, also, mixtures of diblock and triblock copolymers (the latter obtained as end-coupling products of two diblock molecules of the mixture), composed of (a) monodisperse majority block(s) of poly(styrene) (PS) and a polydisperse...

Phase behavior of diblock copolymer/star-shaped polymer thin film mixtures.

Science.gov (United States)

Zhao, Junnan; Sakellariou, Georgios; Green, Peter F

2016-05-07

We investigated the phase behavior of thin film, thickness h≈ 100 nm, mixtures of a polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer with star-shaped polystyrene (SPS) molecules of varying functionalities f, where 4 ≤f≤ 64, and molecular weights per arm Marm. The miscibility of the system and the surface composition varied appreciably with Marm and f. For large values of Marm, regardless of f, the miscibility of the system was qualitatively similar to that of linear chain PS/PS-b-P2VP mixtures - the copolymer chains aggregate to form micelles, each composed of an inner P2VP core and PS corona, which preferentially segregate to the free surface. On the other hand, for large f and small Marm, SPS molecules preferentially resided at the free surface. Moreover, blends containing SPS molecules with the highest values of f and lowest values of Marm were phase separated. These observations are rationalized in terms of competing entropic interactions and the dependence of the surface tension of the star-shaped molecules on Marm and f.

Damping of Mechanical Waves with Styrene/Butadiene Rubber Filled with Polystyrene Particle: Effects of Particles Size and Wave Frequency

Directory of Open Access Journals (Sweden)

M. Haghgo

2007-08-01

Full Text Available Utilizing polymeric materials for damping mechanical waves is of great importance in various fields of applications such as military camouflage, prevention of structural vibrational energy transfer, and noise attenuation. This ability originates from segmental dynamics of chain-like polymer molecules. Damping properties of styrene-butadiene rubbercontaining 10 wt% of monosize polystyrene particles with different diameters (from 80 nm to 500 μm was investigated in the frequency range of vibration, sound, and ultrasound via dynamic mechanical thermal analysis, normalsound adsorption test, and ultrasound attenuation coefficient measurement. The obtained results indicated that for different systems, containing different sizes of polystyrene particles, the area under the damping curve does not show significant change comparing to the neat SBR in the frequency range studied. However, addition of polystyrene particles, specifically nanosized particles, resulted in emergence of a secondary glass transition temperature which could be attributed to the modified dynamics of a layer of matrix molecules near the surface of PS particles. In the range of sound frequency, 0.5 to 6.3 kHz, the maximum damping was observed for the system containing polystyrene nanoparticles. However the single damping curve of neat SBR was separated into two or even three distinct curves owing to the presence of the particles. The maximum damping in the ultrasound frequency range was found for the system containing 0.5 mm polystyrene particles. This is attributed to different contributions from matrix chains dynamics and the reflection of mechanical waves from particles-matrix interface at different frequency ranges. On other words, the increase in the glass transition temperature of the elastomeric matrix phase with increasing the mechanical wave frequency causes a reduction in the contribution from matrix chains dynamics while the contribution due to diffraction from dispersed

Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (Postprint)

National Research Council Canada - National Science Library

Drazowski, Daniel B; Lee, Andre; Haddad, Timothy S

2007-01-01

Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (preprint)

National Research Council Canada - National Science Library

Drazkowski, Daniel B; Lee, Andre; Haddad, Timothy S

2006-01-01

Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition

Energy Technology Data Exchange (ETDEWEB)

Hickey, Robert J.; Gillard, Timothy M.; Irwin, Matthew T.; Morse, David C.; Lodge, Timothy P.; Bates, Frank S. (UMM)

2016-10-13

We have established the existence of a line of congruent first-order lamellar-to-disorder (LAM–DIS) transitions when appropriate amounts of poly(cyclohexylethylene) (C) and poly(ethylene) (E) homopolymers are mixed with a corresponding compositionally symmetric CE diblock copolymer. The line of congruent transitions, or the congruent isopleth, terminates at the bicontinuous microemulsion (BμE) channel, and its trajectory appears to be influenced by the critical composition of the C/E binary homopolymer blend. Blends satisfying congruency undergo a direct LAM–DIS transition without passing through a two-phase region. We present complementary optical transmission, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical spectroscopy (DMS) results that establish the phase behavior at constant copolymer volume fraction and varying C/E homopolymer volume ratios. Adjacent to the congruent composition at constant copolymer volume fraction, the lamellar and disordered phases are separated by two-phase coexistence windows, which converge, along with the line of congruent transitions, at an overall composition in the phase prism coincident with the BμE channel. Hexagonal and cubic (double gyroid) phases occur at higher diblock copolymer concentrations for asymmetric amounts of C and E homopolymers. These results establish a quantitative method for identifying the detailed phase behavior of ternary diblock copolymer–homopolymer blends, especially in the vicinity of the BμE.

Diblock Copolymer/Layered Silicate Nanocomposite Thin Film Stability

Science.gov (United States)

Limary, Ratchana; Green, Peter

2000-03-01

The stability of thin film symmetric diblock copolymers blended with layered silicate nanocomposites were examined using a combination of optical microscopy, atomic force microscopy (AFM), and X-ray diffraction (XRD). Two cases were examined PS-b-PMMA (polystyrene-b-polymethylacrylate) blended with montmorillonite stoichiometrically loaded with alkyl ammonium ions, OLS(S), and PS-b-PMMA blended with montmorillonite loaded with excess alkyl ammonium ions, OLS(E). XRD spectra show an increase in the gallery spacing of the OLSs, indicating that the copolymer chains have intercalated the layered silicates. AFM images reveal a distinct difference between the two nanocomposite thin films: regions in the vicinity of OLS(S) aggregates were depleted of material, while in the vicinity of OLS(E) aggregates, dewetting of the substrate occurred. We show that the stability of the copolymer/OLS nanocomposite films is determined by the enthalpic driving force associated with intercalation of the copolymer chains into the galleries of the modified OLS layers and by the substrate/organic modifier interactions.

Spontaneous Evolution of Nanostructure in Composite Films Consisting of Mixtures of Two Different Block Copolymer Micelles

Science.gov (United States)

Kim, Sehee; Char, Kookheon; Sohn, Byeong-Hyeok

2010-03-01

Diblock copolymers consisting of two immiscible polymer blocks covalently bonded together form various self-assembled nanostructures such as spheres, cylinders, and lamellae in bulk phase. In a selective solvent, however, they assemble into micelles with soluble corona brushes and immiscible cores. Both polystyrene-poly(4-vinylpyridine) (PS-b-P4VP) and polystyrene-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymers form micelles with PS coronas and P4VP or P2VP cores in a PS selective solvent (toluene). By varying the mixture ratio between PS-b-P4VP and PS-b-P2VP, composite films based on the micellar mixtures of PS-b-P4VP and PS-b-P2VP were obtained by spin-coating, followed by the solvent annealing with tetrahydrofuran (THF) vapor. Since THF is a solvent for both PS and P2VP blocks and, at the same time, a non-solvent for the P4VP block, PS-P2VP micelles transformed to lamellar multilayers while PS-P4VP micelles remained intact during the THF annealing. The spontaneous evolution of nanostructure in composite films consisting of lamellae layers with BCP micelles were investigated in detail by cross-sectional TEM and AFM.

Nanostructured poly(styrene-b-butadiene-b-styrene) (SBS) membranes for the separation of nitrogen from natural gas

Energy Technology Data Exchange (ETDEWEB)

Buonomenna, Maria Giovanna; Golemme, Giovanni [Department of Chemical Engineering and Materials, University of Calabria, and Consorzio INSTM, Rende (Italy); Tone, Caterina Maria; De Santo, Maria Penelope; Ciuchi, Federica [IPCF-CNR UOS Cosenza, c/o Physics Department, University of Calabria, Rende (Italy); Perrotta, Enrico [Department of Ecology, University of Calabria, Rende (Italy)

2012-04-24

The preparation and characterization of new, tailor-made polymeric membranes using poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymers for gas separation are reported. Structural differences in the copolymer membranes, obtained by manipulation of the self-assembly of the block copolymers in solution, are characterized using atomic force microscopy, transmission electron microscopy, and the transport properties of three gases (CO{sub 2}, N{sub 2}, and CH{sub 4}). The CH{sub 4}/N{sub 2} ideal selectivity of 7.2, the highest value ever reported for block copolymers, with CH{sub 4} permeability of 41 Barrer, is obtained with a membrane containing the higher amount of polybutadiene (79 wt%) and characterized by a hexagonal array of columnar polystyrene cylinders normal to the membrane surface. Membranes with such a high separation factor are able to ease the exploitation of natural gas with high N{sub 2} content. The CO{sub 2}/N{sub 2} ideal selectivity of 50, coupled with a CO{sub 2} permeability of 289 Barrer, makes SBS a good candidate for the preparation of membranes for the post-combustion capture of carbon dioxide. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes

International Nuclear Information System (INIS)

Zhang, Bo; Edwards, Brian J.

2015-01-01

A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes

The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes.

Science.gov (United States)

Zhang, Bo; Edwards, Brian J

2015-06-07

A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes.

Final report for grant: DE-FG02-93ER45481 [Polymers at engineered interfaces

International Nuclear Information System (INIS)

Rafailovich, Miriam; Sokolov, Jonathan

2000-01-01

Studies have been made of polymer interfaces, self-assembly of micelles at surfaces, phase separation in blends, diffusion and dewetting at and near interfaces, and nanomechanical properties of thin films. The main projects are summarized under the following topics: dislocations in lamellar diblock structures, effects of surface tension; compliance measurements and profiles of end-grafted polystyrene in solution observed by atomic force microscopy and neutron reflectivity; self-assembly of diblock polymer micelles from solution; dewetting dynamics; polymers on patterned surfaces; Flory-Huggins interaction parameter for polystyrene/poly-2-vinylpyridine (PS/P 4 VP) blends; phase separation-induced patterns in dPS/PVME and dPEP/PEP blends; and high-resolution lateral imaging studies of phase separation and dewetting by scanning transmission X-ray microscopy (STXM) and photoemission electron microscopy (PEEM)

Patterned Diblock Co-Polymer Thin Films as Templates for Advanced Anisotropic Metal Nanostructures.

Science.gov (United States)

Roth, Stephan V; Santoro, Gonzalo; Risch, Johannes F H; Yu, Shun; Schwartzkopf, Matthias; Boese, Torsten; Döhrmann, Ralph; Zhang, Peng; Besner, Bastian; Bremer, Philipp; Rukser, Dieter; Rübhausen, Michael A; Terrill, Nick J; Staniec, Paul A; Yao, Yuan; Metwalli, Ezzeldin; Müller-Buschbaum, Peter

2015-06-17

We demonstrate glancing-angle deposition of gold on a nanostructured diblock copolymer, namely polystyrene-block-poly(methyl methacrylate) thin film. Exploiting the selective wetting of gold on the polystyrene block, we are able to fabricate directional hierarchical structures. We prove the asymmetric growth of the gold nanoparticles and are able to extract the different growth laws by in situ scattering methods. The optical anisotropy of these hierarchical hybrid materials is further probed by angular resolved spectroscopic methods. This approach enables us to tailor functional hierarchical layers in nanodevices, such as nanoantennae arrays, organic photovoltaics, and sensor electronics.

Small angle X-ray scattering study of thermodynamic and conformational changes in ion-containing symmetric diblock copolymers

Energy Technology Data Exchange (ETDEWEB)

Gunkel, Ilja [Max Planck Institute of Microstructure Physics, Halle (Germany); Institute of Physics, Martin Luther University Halle Wittenberg, Halle (Germany); Thurn-Albrecht, Thomas [Institute of Physics, Martin Luther University Halle Wittenberg, Halle (Germany)

2010-07-01

We present temperature-dependent SAXS measurements on two different symmetric block copolymers with added salt (lithiumtriflate, LiCF{sub 3}SO{sub 3}). For both studied systems, polystyrene-b-poly-2-vinylpyridine (PS-b-P2VP) and Polystyrene-b-Polyethyleneoxide (PS-b-PEO), the salt selectively dissolved in one block leading to large increases of the order-disorder transition temperatures (T{sub ODT}). In addition, the lamellar thickness of these ion-containing block copolymers nontrivially changed above a certain salt concentration - in PS-b-P2VP the lamellae became thicker whereas their thickness decreased in PS-b-PEO. Using basic arguments of the thermodynamics of block copolymers we were able to separate the ion-induced increase of T{sub ODT} due to a higher incompatibility between the different blocks from changes in the thickness of the lamellae at T{sub ODT} resulting from changes in the conformation of the ion-containing blocks.

Investigating self-assembly and metal nanoclusters in aqueous di-block copolymers solutions

CERN Document Server

Lo Celso, F; Triolo, R; Triolo, A; Strunz, P; Bronstein, L; Zwanziger, J; Lin, J S

2002-01-01

Self-assembling properties of di-block copolymers/ surfactant hybrids in aqueous solution can be exploited to obtain metal nanoparticles stable dispersion. Results will be presented here for polystyrene-block-poly(ethylene oxide) solutions. A SANS structural investigation has been performed over different molecular weights of both hydrophilic and hydrophobic block, by varying temperature and concentration of the copolymer. A SAXS characterization of micellar systems containing Pt nanoparticles is reported. (orig.)

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

Institute of Scientific and Technical Information of China (English)

Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

2000-01-01

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

Synthesis and solution properties of PCL-b-PHPMA diblock copolymers containing stable nitroxyl radicals

Czech Academy of Sciences Publication Activity Database

Petrova, Svetlana; Klepac, Damir; Konefal, Rafal; Kereiche, S.; Kováčik, L.; Filippov, Sergey K.

2016-01-01

Roč. 49, č. 15 (2016), s. 5407-5417 ISSN 0024-9297 R&D Projects: GA MŠk(CZ) LH15213 Institutional support: RVO:61389013 Keywords : PCL-b-PHPMA diblock copolymers * TEMPO * EPR spectroscodpy Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.835, year: 2016

Morphological transformations of diblock copolymers in binary solvents: A simulation study

Science.gov (United States)

Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

2017-12-01

Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on the morphological transformation depending on the fraction of the selective solvent C S2, the concentration of the polymer C p , and the polymer-solvent interactions ɛ ij ( i = A, B; j = S1, S2). Morphology diagrams are constructed as functions of C p , C S2, and/or ɛ AS2. The copolymer morphological sequence from dissolved → sphere → rod → ring/cage → vesicle is obtained upon increasing C S2 at a fixed C p . This morphology sequence is consistent with previous experimental observations. It is found that the selectivity of the selective solvent affects the self-assembled microstructure significantly. In particular, when the interaction ɛ BS2 is negative, aggregates of stacked lamellae dominate the diagram. The mechanisms of aggregate transformation and the formation of stacked lamellar aggregates are discussed by analyzing variations of the average contact numbers of the A or B monomers with monomers and with molecules of the two types of solvent, as well as the mean square end-to-end distances of chains. It is found that the basic morphological sequence of spheres to rods to vesicles and the stacked lamellar aggregates result from competition between the interfacial energy and the chain conformational entropy. Analysis of the vesicle structure reveals that the vesicle size increases with increasing C p or with decreasing C S2, but remains almost unchanged with variations in ɛ AS2.

Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

NARCIS (Netherlands)

Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

2002-01-01

Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86

Quantitative analysis of styrene butadiene copolymers using S-SIMS and LA-FTICRMS

International Nuclear Information System (INIS)

Ruch, D.; Boes, C.; Zimmer, R.; Muller, J.F.; Migeon, H.-N.

2003-01-01

Styrene butadiene copolymers (SBR) have been analyzed by static secondary ion mass spectrometry (S-SIMS) and laser ablation Fourier transform ion cyclotron resonance mass spectrometry (LA-FTICRMS) to obtain quantitative information based on specific peaks knowing that the complication of this system is that there are no characteristic SIMS peaks unique to each styrene and butadiene monomer. So, to overcome this problem, a silver deposition has been applied into polystyrene (PS), butadiene rubber (BR) and SBR. By this way, new secondary ions are detected in particular silver cationized butadiene and styrene monomers at m/z 161/163 and 211/213, respectively. The LA-FTICRMS experiments do not require pre-treatment. At high laser power density, UV photons (193, 266 and 355 nm) allow to detect directly the styrene and butadiene ions at m/z 104 and 54, respectively. Using these SIMS and LA-FTICRMS peaks, it is possible to obtain quantitative results. However, the silver coating in the SIMS experiment seems to have a great influence on the obtention of quantitative information. For LA-FTICRMS experiments, the best results seem to be obtained at the 355 nm wavelength

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

Science.gov (United States)

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.

Two-dimensional phase separated structures of block copolymers on solids

Science.gov (United States)

Sen, Mani; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori; Ribbe, Alexander

The fundamental, yet unsolved question in block copolymer (BCP) thin films is the self-organization process of BCPs at the solid-polymer melt interface. We here focus on the self-organization processes of cylinder-forming polystyrene-block-poly (4-vinylpyridine) diblock copolymer and lamellar-forming poly (styrene-block-butadiene-block-styrene) triblock copolymer on Si substrates as model systems. In order to reveal the buried interfacial structures, the following experimental protocols were utilized: the BCP monolayer films were annealed under vacuum at T>Tg of the blocks (to equilibrate the melts); vitrification of the annealed BCP films via rapid quench to room temperature; subsequent intensive solvent leaching (to remove unadsorbed chains) with chloroform, a non-selective good solvent for the blocks. The strongly bound BCP layers were then characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle X-ray scattering, and X-ray reflectivity. The results showed that both blocks lie flat on the substrate, forming the two-dimensional, randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. Acknowledgement of financial support from NSF Grant (CMMI -1332499).

A theoretical and simulation study of the self-assembly of a binary blend of diblock copolymers

KAUST Repository

Padmanabhan, Poornima

2012-01-01

Pure diblock copolymer melts exhibit a narrow range of conditions at which bicontinuous and cocontinuous phases are stable; such conditions and the morphology of such phases can be tuned by the use of additives. In this work, we have studied a bidisperse system of diblock copolymers using theory and simulation. In particular, we elucidated how a short, lamellar-forming diblock copolymer modifies the phase behavior of a longer, cylinder-forming diblock copolymer. In a narrow range of intermediate compositions, self-consistent field theory predicts the formation of a gyroid phase although particle-based simulations show that three phases compete: the gyroid phase, a disordered cocontinuous phase, and the cylinder phase, all having free energies within error bars of each other. Former experimental studies of a similar system have yielded an unidentified, partially irregular bicontinuous phase, and our simulations suggest that at such conditions the formation of a partially transformed network phase is indeed plausible. Close examination of the spatial distribution of chains reveals that packing frustration (manifested by chain stretching and low density spots) occurs in the majority-block domains of the three competing phases simulated. In all cases, a double interface around the minority-block domains is also detected with the outer one formed by the short chains, and the inner one formed by the longer chains. © 2012 American Institute of Physics.

Chain confinement, phase transitions, and lamellar structure in semicrystalline polymers, polymer blends and polymer nanocomposites

Science.gov (United States)

Chen, Huipeng

and is applied to the iPS/atactic polystyrene, aPS, blends. The fractions of MAF inside and outside the lamellar stacks were quantified for the first time. For A/B binary polymer blends, it has been reported that if B is already crystalline, the crystalline fraction would serve as a restriction on the subsequent growth of the crystallizable partner A, while amorphous fraction could be diffused from the crystalline growth front of the crystallizing A component. Considering the effect of RAF on binary blends, a new concept is provided: like the crystals, the RAF of one polymer component may inhibit the growth of crystals of the other blend partner. The non-isothermal crystallization of PET/poly(lactic acid), PLA, blends were investigated and the results confirmed the new concept is correct: PET forms a large amount of RAF and inhibits crystal formation in PLA. Then, we broadened the concept of RAF and investigated the RAF in recent 'hot' materials, polymer nanocomposites. It was found the fraction of RAF greatly increased with a small amount of multi-wall carbon nanotubes, MWCNT, loading in PET electrospun, ES, fibers. A general model is given for polymer ES fibers with MWCNTs: the addition of MWCNTs causes polymer chains in the ES fibers to become more extended, (ie, more stretched), resulting in more confinement of PET chains and an increase in the RAF.

Structural and rectifying junction properties of self-assembled ZnO nanoparticles in polystyrene diblock copolymers on (1 0 0)Si substrates

Science.gov (United States)

Ali, H. A.; Iliadis, A. A.; Martinez-Miranda, L. J.; Lee, U.

2006-06-01

The structural and electronic transport properties of self-assembled ZnO nanoparticles in polystyrene-acrylic acid, [PS] m/[PAA] n, diblock copolymer on p-type (1 0 0)Si substrates are reported for the first time. Four different block repeat unit ratios ( m/ n) of 159/63, 139/17,106/17, and 106/4, were examined in order to correlate the physical parameters (size, density) of the nanoparticles with the copolymer block lengths m and n. We established that the self-assembled ZnO nanoparticle average size increased linearly with minority block length n, while the average density decreased exponentially with majority block length m. Average size varied from 20 nm to 250 nm and average density from 3.5 × 10 7 cm -2 to 1 × 10 10 cm -2, depending on copolymer parameters. X-ray diffraction studies showed the particles to have a wurtzite crystal structure with the (1 0 0) being the dominant orientation. Room temperature current-voltage characteristics measured for an Al/ZnO-nanocomposite/Si structure exhibited rectifying junction properties and indicated the formation of Al/ZnO-nanocomposite Schottky type junction with a barrier height of 0.7 V.

Gelation of Photonic Microdomain Structures Formed in Semi-Dilute Solutions of Ultra-High-Molecular-Weight Polystyrene-b-Polybutadiene with Various Polybutadiene Contents

International Nuclear Information System (INIS)

Okamoto, S; Ito, S; Ando, K; Mouri, M; Ikeda, A; Hasegawa, H; Koshikawa, N

2010-01-01

Well-ordered microdomain structures were obtained in semi-dilute solutions and successfully stabilized by gelation. We used polystyrene-b-polybutadiene (PS-b-PB) diblock copolymer with the weight-averaged molecular weight varying from several hundred thousands to millions g/mol. The solutions had iridescent colors because the domain spacing is on the order of the wavelength of visible light. As the structures are susceptible to distortion by flow or vibration, structural fixation was carried out by gelation. The polybutadiene used has the microstructure of 1,2-linkage and hence the chains can be cross-linkable. The Small-Angle X-ray Scattering and the UV-vis spectroscopic measurements showed that in the case of PS-b-PBs with the PB volume fraction, φ PB , greater than about 50 vol % the microdomain structures were successfully fixed by gelation, while largely distorted in the case of those with φ PB < ca. 50 vol %. The SAXS scattering intensities were quantitatively analyzed by the scattering functions numerically calculated based on the one- and two-dimensional paracrystal theories and on the concentration fluctuation between the polymers and the solvent molecules.

A new process for fabricating nanodot arrays on selective regions with diblock copolymer thin film

Energy Technology Data Exchange (ETDEWEB)

Park, Dae-Ho [Department of Materials Science and Engineering, Polymer Research Institute, Pohang University of Science and Technology, San 31, Hyoja-Dong, Nam-Gu, Pohang 790-784 (Korea, Republic of)

2007-09-12

A procedure for micropatterning a single layer of nanodot arrays in selective regions is demonstrated by using thin films of polystyrene-b-poly(t-butyl acrylate) (PS-b-PtBA) diblock copolymer. The thin-film self-assembled into hexagonally arranged PtBA nanodomains in a PS matrix on a substrate by solvent annealing with 1,4-dioxane. The PtBA nanodomains were converted into poly(acrylic acid) (PAA) having carboxylic-acid-functionalized nanodomains by exposure to hydrochloric acid vapor, or were removed by ultraviolet (UV) irradiation to generate vacant sites without any functional groups due to the elimination of PtBA domains. By sequential treatment with aqueous sodium bicarbonate and aqueous zinc acetate solution, zinc cations were selectively loaded only on the carboxylic-acid-functionalized nanodomains prepared via hydrolysis. Macroscopic patterning through a photomask via UV irradiation, hydrolysis, sequential zinc cation loading and calcination left a nanodot array of zinc oxide on a selectively UV-shaded region.

Self-Assembly of Diblock Molecular Polymer Brushes in the Spherical Confinement of Nanoemulsion Droplets.

Science.gov (United States)

Steinhaus, Andrea; Pelras, Théophile; Chakroun, Ramzi; Gröschel, André H; Müllner, Markus

2018-05-02

Understanding the self-assembly behavior of polymers of various topologies is key to a reliable design of functional polymer materials. Self-assembly under confinement conditions emerges as a versatile avenue to design polymer particles with complex internal morphologies while simultaneously facilitating scale-up. However, only linear block copolymers have been studied to date, despite the increasing control over macromolecule composition and architecture available. This study extends the investigation of polymer self-assembly in confinement from regular diblock copolymers to diblock molecular polymer brushes (MPBs). Block-type MPBs with polystyrene (PS) and polylactide (PLA) compartments of different sizes are incorporated into surfactant-stabilized oil-in-water (chloroform/water) emulsions. The increasing confinement in the nanoemulsion droplets during solvent evaporation directs the MPBs to form solid nano/microparticles. Microscopy studies reveal an intricate internal particle structure, including interpenetrating networks and axially stacked lamellae of PS and PLA, depending on the PS/PLA ratio of the brushes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Precipitation of lamellar gold nanocrystals in molten polymers

International Nuclear Information System (INIS)

Palomba, M.; Carotenuto, G.

2016-01-01

Non-aggregated lamellar gold crystals with regular shape (triangles, squares, pentagons, etc.) have been produced by thermal decomposition of gold chloride (AuCl) molecules in molten amorphous polymers (polystyrene and poly(methyl methacrylate)). Such covalent inorganic gold salt is high soluble into non-polar polymers and it thermally decomposes at temperatures compatible with the polymer thermal stability, producing gold atoms and chlorine radicals. At the end of the gold precipitation process, the polymer matrix resulted chemically modified because of the partial cross-linking process due to the gold atom formation reaction.

Nanoscale protein arrays of rich morphologies via self-assembly on chemically treated diblock copolymer surfaces

International Nuclear Information System (INIS)

Song Sheng; Milchak, Marissa; Zhou Hebing; Lee, Thomas; Hanscom, Mark; Hahm, Jong-in

2013-01-01

Well-controlled assembly of proteins on supramolecular templates of block copolymers can be extremely useful for high-throughput biodetection. We report the adsorption and assembly characteristics of a model antibody protein to various polystyrene-block-poly(4-vinylpyridine) templates whose distinctive nanoscale structures are obtained through time-regulated exposure to chloroform vapor. The strong adsorption preference of the protein to the polystyrene segment in the diblock copolymer templates leads to an easily predictable, controllable, rich set of nanoscale protein morphologies through self-assembly. We also demonstrate that the chemical identities of various subareas within individual nanostructures can be readily elucidated by investigating the corresponding protein adsorption behavior on each chemically distinct area of the template. In our approach, a rich set of intricate nanoscale morphologies of protein arrays that cannot be easily attained through other means can be generated straightforwardly via self-assembly of proteins on chemically treated diblock copolymer surfaces, without the use of clean-room-based fabrication tools. Our approach provides much-needed flexibility and versatility for the use of block copolymer-based protein arrays in biodetection. The ease of fabrication in producing well-defined and self-assembled templates can contribute to a high degree of versatility and simplicity in acquiring an intricate nanoscale geometry and spatial distribution of proteins in arrays. These advantages can be extremely beneficial both for fundamental research and biomedical detection, especially in the areas of solid-state-based, high-throughput protein sensing. (paper)

Mesomorphic phase behaviour of low molar mass PEP-PDMS diblock copolymers synthesized by anionic polymerization

International Nuclear Information System (INIS)

Vigild, M.E.

1997-10-01

The phase behaviour of low molar mass poly(ethylene-alt-propylene) -poly(dimethylsiloxane) (PEP-PDMS) is investigated in this thesis by the combination of dynamical mechanical spectroscopy (rheology) to measure phase transition temperatures, and small-angle x-ray scattering to identify the morphology of encountered phases. Samples of PEP-PDMS in the range of 0.2-0.7 in volume fraction of PEP are studied. This diblock copolymer system exhibits the three classical phases of lamellar sandwich structure (LAM), hexagonally packed cylinders (HEX), and spheres arranged on a body centered cubic lattice (BCC). Furthermore the gyroid phase (Ia3d symmetry) of two interpenetrating networks was also identified as a stable phase of the PEP-PDMS system. Time resolved measurements of small-angle neutron scattering in tandem with simultaneous in-situ rheological measurements are performed on samples showing transitions between different ordered phases. The identification of especially the BCC and gyroid phases from scattering experiments is treated. By performing mesoscopic crystallographic measurements using a custom built goniometer it was unambiguously shown that the application of shear to an unoriented powder-like sample introduces uniaxial orientation of the gyroid phase. The orientation of the ordered phase is otherwise random, causing a two-dimensional powder. Finally this dissertation presents a discussion of relevant parameters for the description of diblock copolymer phase behaviour together with descriptions of anionic polymerization for the synthesis of copolymers, and various experimental techniques for the characterization of diblocks. (au)

Mesomorphic phase behaviour of low molar mass PEP-PDMS diblock copolymers synthesized by anionic polymerization

Energy Technology Data Exchange (ETDEWEB)

Vigild, M.E.

1997-10-01

The phase behaviour of low molar mass poly(ethylene-alt-propylene) -poly(dimethylsiloxane) (PEP-PDMS) is investigated in this thesis by the combination of dynamical mechanical spectroscopy (rheology) to measure phase transition temperatures, and small-angle x-ray scattering to identify the morphology of encountered phases. Samples of PEP-PDMS in the range of 0.2-0.7 in volume fraction of PEP are studied. This diblock copolymer system exhibits the three classical phases of lamellar sandwich structure (LAM), hexagonally packed cylinders (HEX), and spheres arranged on a body centered cubic lattice (BCC). Furthermore the gyroid phase (Ia3d symmetry) of two interpenetrating networks was also identified as a stable phase of the PEP-PDMS system. Time resolved measurements of small-angle neutron scattering in tandem with simultaneous in-situ rheological measurements are performed on samples showing transitions between different ordered phases. The identification of especially the BCC and gyroid phases from scattering experiments is treated. By performing mesoscopic crystallographic measurements using a custom built goniometer it was unambiguously shown that the application of shear to an unoriented powder-like sample introduces uniaxial orientation of the gyroid phase. The orientation of the ordered phase is otherwise random, causing a two-dimensional powder. Finally this dissertation presents a discussion of relevant parameters for the description of diblock copolymer phase behaviour together with descriptions of anionic polymerization for the synthesis of copolymers, and various experimental techniques for the characterization of diblocks. (au). 9 tabs., 40 ills., 81 refs.

Theoretical study of the self-assembly of Janus Bottlebrush Polymers from A-Branch-B Diblock Macromonomers

Science.gov (United States)

Gadelrab, Karim; Alexander-Katz, Alfredo; LaboratoryTheoretical Soft Materials Team

The self-assembly of block copolymers BCP has provided an impressive control over the nanoscale structure of soft matter. While the main focus of the research in the field has been directed towards simple linear diblocks, the development of advanced polymer architecture provided improved performance and access to new structures. In particular, bottlebrush BCPs (BBCPs) have interesting characteristics due to their dense functionality, high molecular weight, low levels of entanglement, and tendency to efficiently undergo rapid bulk phase separation. In this work, we are interested in theoretically studying the self-assembly of Janus-type ``A-branch-B'' BBCPs where A and B blocks can phase separate with the bottlebrush polymer backbone serving as the interface between the two blocks. Hence, the polymer backbone adds an extra constraint on the equilibrium spacing between neighboring linear diblock chains. In this regard, the segment length of the backbone separating the AB junctions has a direct effect of the observed domain spacing and effective segregation strength of the AB blocks. We employ self-consistent field theoretic SCFT simulations to capture the effect of volume fraction of different constituents and construct a phase diagram of the accessible morphologies of these BBCPs.

Dilute solutions and phase behavior of polydisperse A-b-(A-co-B) diblock copolymers

Czech Academy of Sciences Publication Activity Database

Gromadzki, Daniel; Lokaj, Jan; Šlouf, Miroslav; Štěpánek, Petr

2009-01-01

Roč. 50, č. 11 (2009), s. 2451-2459 ISSN 0032-3861 Institutional research plan: CEZ:AV0Z40500505 Keywords : diblock copolymer * dilute solution properties * microphase separation Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.573, year: 2009

Magnetic field alignment of coil-coil diblock copolymers and blends via intrinsic chain anisotropy

Science.gov (United States)

Rokhlenko, Yekaterina; Majewski, Pawel; Larson, Steven; Yager, Kevin; Gopalan, Padma; Avgeropoulos, Apostolos; Chan, Edwin; Osuji, Chinedum

Magnetic fields can control alignment of self-assembled soft materials such as block copolymers provided there is a suitably large magnetic susceptibility anisotropy present in the system. Recent results have highlighted the existence of a non-trivial intrinsic anisotropy in coil-coil diblock copolymers, specifically in lamellar-forming PS-b-P4VP, which enables alignment at field strengths of a few tesla in systems lacking mesogenic components. Alignment is predicated on correlation in the orientation of end-end vectors implied by the localization of block junctions at the microdomain interface and is observed on cooling across the order-disorder transition in the presence of the field. For appropriate combinations of field strength and grain size, we can leverage intrinsic chain anisotropy to magnetically direct self-assembly of many non-mesogenic systems, including other coil-coil BCPs like PS-b-PDMS and PS-b-PMMA, blends of BCPs of disparate morphologies and MWs, and blends of BCPs with homopolymers. This is noteworthy as blends of PS-b-P4VP with PEO provide a route to form functional materials such as nanoporous films by dissolution of PEO, or aligned ion conduction materials. We survey these various systems using TEM and in-situ X-ray scattering to study the phase behavior and temperature-, time- and field- dependent dynamics of alignment.

Styrene-butadiene-styrene copolymer compatibilized carbon black/polypropylene/polystyrene composites with tunable morphology, electrical conduction and rheological stabilities.

Science.gov (United States)

Song, Yihu; Xu, Chunfeng; Zheng, Qiang

2014-04-21

We report a facile kinetic strategy in combination with styrene-butadiene-styrene (SBS) copolymer compatibilizers for preparing carbon black (CB) filled immiscible polypropylene (PP)/polystyrene (PS) (1/1) blends with finely tuned morphologies and show the important role of location and migration of CB nanoparticles in determining the electrical conductivity and rheological behaviour of the composites. A novel method of mixing a SBS/CB (5/3) masterbatch with the polymers allowed producing composites with CB aggregates dispersed partially in the unfavorable PP phase and partially in the PP side of the interface to exhibit diverse phase connectivity and electrical conductivity depending on the compounding sequences. A cocontinuous morphology with CB enrichment along the interface was formed in the composite prepared by mixing the SBS/CB masterbatch with the premixed PP/PS blend, giving rise to a highest electrical conductivity and dynamic moduli at low frequencies. On the other hand, mixing the masterbatch with one and then with another polymer yielded droplet (PS)-in-matrix (filled PP) composites. The composites underwent phase coalescence and CB redistribution accompanied by marked dynamic electrical conduction and modulus percolations as a function of time during thermal annealing at 180 °C. The composites with the initial droplet-in-matrix morphology progressed anomalously into the cocontinuous morphology, reflecting a common mechanism being fairly nonspecific for understanding the processing of filled multicomponent composites with tailored performances of general concern.

Activated Porous Carbon Spheres with Customized Mesopores through Assembly of Diblock Copolymers for Electrochemical Capacitor.

Science.gov (United States)

Tang, Jing; Wang, Jie; Shrestha, Lok Kumar; Hossain, Md Shahriar A; Alothman, Zeid Abdullah; Yamauchi, Yusuke; Ariga, Katsuhiko

2017-06-07

A series of porous carbon spheres with precisely adjustable mesopores (4-16 nm), high specific surface area (SSA, ∼2000 m 2 g -1 ), and submicrometer particle size (∼300 nm) was synthesized through a facile coassembly of diblock polymer micelles with a nontoxic dopamine source and a common postactivation process. The mesopore size can be controlled by the diblock polymer, polystyrene-block-poly(ethylene oxide) (PS-b-PEO) templates, and has an almost linear dependence on the square root of the degree of polymerization of the PS blocks. These advantageous structural properties make the product a promising electrode material for electrochemical capacitors. The electrochemical capacitive performance was studied carefully by using symmetrical cells in a typical organic electrolyte of 1 M tetraethylammonium tetrafluoroborate/acetonitrile (TEA BF 4 /AN) or in an ionic liquid electrolyte of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF 4 ), displaying a high specific capacitance of 111 and 170 F g -1 at 1 A g -1 , respectively. The impacts of pore size distribution on the capacitance performance were thoroughly investigated. It was revealed that large mesopores and a relatively low ratio of micropores are ideal for realizing high SSA-normalized capacitance. These results provide us with a simple and reliable way to screen future porous carbon materials for electrochemical capacitors and encourage researchers to design porous carbon with high specific surface area, large mesopores, and a moderate proportion of micropores.

Synthesis by ATRP of poly(ethylene-co-butylene)-block-polystyrene, poly(ethylene-co-butylene)-block-poly(4-acetoxystyrene) and its hydrolysis product poly(ethylene-co-butylene)-block-poly(hydroxystyrene)

DEFF Research Database (Denmark)

Jankova, Katja; Kops, Jørgen; Chen, Xianyi

1999-01-01

Diblock copolymers of poly(ethylene-co-butylene) and polystyrene or poly(4-acetoxystyrene) are synthesized by atom transfer radical polymerization (ATRP) using a 2-bromopropionic ester macroinitiator prepared from commercial monohydroxyl functional narrow dispersity hydrogenated polybutadiene...

Interactions of poly(tert-butyl acrylate)-poly(styrene) diblock copolymers with lipids at the air-water interface.

Science.gov (United States)

Mudgil, Poonam; Dennis, Gary R; Millar, Thomas J

2006-08-29

Diblock copolymers with hydrophilic poly(tert-butyl acrylate) (PtBA) and hydrophobic poly(styrene) (PS) blocks were synthesized with a view to use them as a surfactant in tear film for increasing the ocular comfort in dry eye syndrome. Interactions of six PtBA-PS copolymers with four important lipids found in the tear film, namely cholesterol, cholesteryl palmitate, dipalmitoyl phosphatidylcholine, and phosphatidylinositol, were studied at the air-water interface using a Langmuir trough. Thermodynamics of mixing of the copolymers and the lipids in the mixed monolayers was determined by calculating excess free energy of mixing. The diblock copolymers showed repulsive interactions with cholesteol and cholesteryl palmitate, near neutral interactions with dipalmitoyl phosphatidylcholine, and attractive interactions with phosphatidylinositol. The lipids interacted with the PS component of the copolymer. The results indicate that a copolymer with a small hydrophilic group and a big hydrophobic group can be a likely candidate for forming stable interactions with the lipids present in the tear film and hence increase the ocular comfort.

Lateral Order and Self-Organized Morphology of Diblock Copolymer Micellar Films

Directory of Open Access Journals (Sweden)

Jiun-You Liou

2018-05-01

Full Text Available We report the lateral order and self-organized morphology of diblock copolymer polystyrene-block-poly(2-vinylpyridine, P(S-b-2VP, and micelles on silicon substrates (SiOx/Si. These micellar films were prepared by spin coating from polymer solutions of varied concentration of polymer in toluene onto SiOx/Si, and were investigated with grazing-incidence small-angle X-ray scattering (GISAXS and an atomic force microscope (AFM. With progressively increased surface coverage with increasing concentration, loosely packed spherical micelles, ribbon-like nanostructures, and a second layer of spherical micelles were obtained sequentially. Quantitative analysis and simulations of the micellar packing demonstrates that the spatial ordering of the loosely packed spherical micelles altered from short-range order to hexagonal order when the micellar coverage increased from small to moderate densities of the covered surface. At large densities, anisotropic fusion between spherical micelles caused the ribbon-like nanostructures to have a short-range spatial order; the ordering quality of the second layer was governed by the rugged surface of the underlying layer because the valleys between the ribbon-like nanostructures allowed for further deposition of spherical micelles.

Low molecular weight block copolymers as plasticizers for polystyrene

DEFF Research Database (Denmark)

Hansen, Kristoffer Karsten; Nielsen, Charlotte Juel; Hvilsted, Søren

2005-01-01

/mol and minimum polystyrene content of 50 w/w%, which by us is predicted as the limits for solubility of polystyrene-b-alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight...... of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene-b-alkyl is found to be an efficient plasticizer also...... for polystyrene-b-polyisoprene-b-polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene-b-alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene-b-polybutadiene-b-polystyrene and polystyrene-bpoly(propylene glycol...

Shear Alignment of Diblock Copolymers for Patterning Nanowire Meshes

Energy Technology Data Exchange (ETDEWEB)

Gustafson, Kyle T. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2016-09-08

Metallic nanowire meshes are useful as cheap, flexible alternatives to indium tin oxide – an expensive, brittle material used in transparent conductive electrodes. We have fabricated nanowire meshes over areas up to 2.5 cm² by: 1) mechanically aligning parallel rows of diblock copolymer (diBCP) microdomains; 2) selectively infiltrating those domains with metallic ions; 3) etching away the diBCP template; 4) sintering to reduce ions to metal nanowires; and, 5) repeating steps 1 – 4 on the same sample at a 90° offset. We aligned parallel rows of polystyrene-b-poly(2-vinylpyridine) [PS(48.5 kDa)-b-P2VP(14.5 kDa)] microdomains by heating above its glass transition temperature (T_g ≈ 100°C), applying mechanical shear pressure (33 kPa) and normal force (13.7 N), and cooling below T_g. DiBCP samples were submerged in aqueous solutions of metallic ions (15 – 40 mM ions; 0.1 – 0.5 M HCl) for 30 – 90 minutes, which coordinate to nitrogen in P2VP. Subsequent ozone-etching and sintering steps yielded parallel nanowires. We aimed to optimize alignment parameters (e.g. shear and normal pressures, alignment duration, and PDMS thickness) to improve the quality, reproducibility, and scalability of meshes. We also investigated metals other than Pt and Au that may be patterned using this technique (Cu, Ag).

A proton-conducting composite membrane: Sn0.95Al0.05P2O7 and polystyrene-b-poly(ethylene/propylene)-b-polystyrene

International Nuclear Information System (INIS)

Jin, Yongcheng; Hibino, Takashi

2010-01-01

An anhydrous proton conductor, Sn 0.95 Al 0.05 P 2 O 7 (SAPO), composed of polystyrene-b-poly(ethylene/propylene)-b-polystyrene (SEPS), was developed and characterized using morphological, structural, and electrochemical analyses. In the composite membrane with 20 wt% SEPS, a homogeneous distribution of SAPO particles in the matrix was obtained in the thickness range of 65-90 μm, yielding a proton conductivity of 3.4 x 10 -3 S cm -1 at 200 o C, tensile strength of 4.6 MPa and an elongation at break of 711.0% at room temperature. Fuel cell tests verified that the open-circuit voltage was maintained at a constant value of approximately 1 V between 100 and 250 o C. The peak power densities achieved with unhumidified H 2 and air were 77.0 mW cm -2 at 100 o C, 121.0 mW cm -2 at 150 o C, and 163.1 mW cm -2 at 225 o C.

Dye-sensitized PS-b-P2VP-templated nickel oxide films for photoelectrochemical applications

OpenAIRE

Massin, Julien; Bräutigam, Maximilian; Kaeffer, Nicolas; Queyriaux, Nicolas; Field, Martin J.; Schacher, Felix H.; Popp, Jürgen; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin; Artero, Vincent

2015-01-01

Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push–pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material template...

Chain length dependence of the helix orientation in Langmuir-Blodgett monolayers of alpha-helical diblock copolypeptides

NARCIS (Netherlands)

Nguyen, Le-Thu T.; Ardana, Aditya; Vorenkamp, Eltjo J.; ten Brinke, Gerrit; Schouten, Arend J.

2010-01-01

The effect of chain length on the helix orientation of alpha-helical diblock copolypeptides in Langmuir and Langmuir-Blodgett monolayers is reported for the first time. Amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and

Phase transition of LB films of mixed diblock copolymer at the air/water interface

Science.gov (United States)

Seo, Y. S.; Kim, K. S.; Samuilov, V.; Rafailovich, M. H.; Sokolov, J.; Lammertink, Rob G. H.; Vancso, G. J.

2000-03-01

We have studied the morphology of Langmuir blodgett films at the air/water interface of mixed diblock copolymer films. Solutions of poly(styrene-b-ferrocenyldimethylsilane) and PS-b-P2VP mixed in a ratio of 20/80 in chloroform were spread at the air/water interface. The morphology of the films was studied with AFM as a function of the surface pressure and the diblock copolymer molecular weight. The results show that the two diblock copolymers can be induced to mix at the air/water interface with increasing surface pressure. A reversible transition from spherical to cylindrical morphologies is induced in the mixture which can not be observed in films formed of the two components separately. The effective surface phase diagram as a function of block copolymer composition and pressure will be presented.

Conformation and structural changes of diblock copolymers with octopus-like micelle formation in the presence of external stimuli

Science.gov (United States)

Dammertz, K.; Saier, A. M.; Marti, O.; Amirkhani, M.

2014-04-01

External stimuli such as vapours and electric fields can be used to manipulate the formation of AB-diblock copolymers on surfaces. We study the conformational variation of PS-b-PMMA (polystyrene-block-poly(methyl methacrylate)), PS and PMMA adsorbed on mica and their response to saturated water or chloroform atmospheres. Using specimens with only partial polymer coverage, new unanticipated effects were observed. Water vapour, a non-solvent for all three polymers, was found to cause high surface mobility. In contrast, chloroform vapour (a solvent for all three polymers) proved to be less efficient. Furthermore, the influence of an additional applied electric field was investigated. A dc field oriented parallel to the sample surface induces the formation of polymer islands which assemble into wormlike chains. Moreover, PS-b-PMMA forms octopus-like micelles (OLMs) on mica. Under the external stimuli mentioned above, the wormlike formations of OLMs are able to align in the direction of the external electric field. In the absence of an electric field, the OLMs disaggregate and exhibit phase separated structures under chloroform vapour.

Conformation and structural changes of diblock copolymers with octopus-like micelle formation in the presence of external stimuli

International Nuclear Information System (INIS)

Dammertz, K; Saier, A M; Marti, O; Amirkhani, M

2014-01-01

External stimuli such as vapours and electric fields can be used to manipulate the formation of AB-diblock copolymers on surfaces. We study the conformational variation of PS-b-PMMA (polystyrene-block-poly(methyl methacrylate)), PS and PMMA adsorbed on mica and their response to saturated water or chloroform atmospheres. Using specimens with only partial polymer coverage, new unanticipated effects were observed. Water vapour, a non-solvent for all three polymers, was found to cause high surface mobility. In contrast, chloroform vapour (a solvent for all three polymers) proved to be less efficient. Furthermore, the influence of an additional applied electric field was investigated. A dc field oriented parallel to the sample surface induces the formation of polymer islands which assemble into wormlike chains. Moreover, PS-b-PMMA forms octopus-like micelles (OLMs) on mica. Under the external stimuli mentioned above, the wormlike formations of OLMs are able to align in the direction of the external electric field. In the absence of an electric field, the OLMs disaggregate and exhibit phase separated structures under chloroform vapour. (paper)

Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases

KAUST Repository

Ntetsikas, Konstantinos

2017-10-23

The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular weights and narrow polydispersity (Ð < 1.05). In the case of t-BuP2, homopolymers with higher than the theoretical molecular weights and relatively low polydispersity were obtained. On the other hand, in the presence of t-BuP4, the polymerization of styrene was uncontrolled due to the high reactivity of the formed carbanion. The kinetic studies from the polymerization of both monomers showed that the reaction rate follows the order of [t-BuP4]/[sec-BuLi] >>> [t-BuP2]/[sec-BuLi] >> [t-BuP1]/[sec-BuLi] > sec-BuLi. Furthermore, the addition of t-BuP2 and t-BuP1 prior the polymerization of 1,3-butadiene allowed the synthesis of polybutadiene with a high 1,2-microstructure (~45 wt %), due to the delocalization of the negative charge. Finally, the one pot synthesis of well-defined polyester-based copolymers [PS-b-PCL and PS-b-PLLA, PS: Polystyrene, PCL: Poly(ε-caprolactone) and PLLA: Poly(L-lactide)], with predictable molecular weights and a narrow molecular weight distribution (Ð < 1.2), was achieved by sequential copolymerization in the presence of t-BuP2 and t-BuP1.

Stepwise Swelling of a Thin Film of Lamellae-Forming Poly(styrene-b-butadiene) in Cyclohexane Vapor

DEFF Research Database (Denmark)

Di, Zhenyu; Posselt, Dorthe; Smilgies, Detlef-M.

2012-01-01

We investigated the swelling of a thin film of lamellae-forming poly(styrene-b-butadiene) in cyclohexane vapor. The vapor pressure and thus the degree of swelling of the film are increased in a stepwise manner using a custom-built sample cell. The resulting structural changes during and after each...

Lamellar-lamellar phase separation of phospholipid bilayers induced by salting-in/-out effects

Energy Technology Data Exchange (ETDEWEB)

Hishida, Mafumi [Institute for Integrated Cell-Material Sciences, Kyoto University, Kyoto 606-8501 (Japan); Seto, Hideki, E-mail: hideki.seto@kek.jp [KENS and CMRC, Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba 305-0801 (Japan)

2011-01-01

The multilamellar structure of phospholipid bilayers is stabilized by the interactions between bilayers. Although the lamellar repeat distance is uniquely determined at the balance point of interactions between bilayers, a lamellar-lamellar phase separation, where the two phases with different lamellar repeat distance coexist, has been reported in a case of adding a salt to the aqueous solution of lipids. In order to understand the physical mechanism of the lamellar-lamellar phase separation, the effects of adding monovalent salt on the lamellar structure are studied by visual observation and by small-angle X-ray scattering. Further, a theoretical model based on the mean field theory is introduced and it is concluded that the salting-in and -out effects of lipid bilayers trigger the lamellar-lamellar phase separation.

(Quasi-) 2D aggregation of polystyrene-b-dextran at the air-water interface

NARCIS (Netherlands)

Bosker, W.T.E.; Cohen Stuart, M.A.; Norde, W.

2013-01-01

Polystyrene-b-dextran (PS-b-Dextran) copolymers can be used to prepare dextran brushes at solid surfaces, applying Langmuir–Blodgett deposition. When recording the interfacial pressure versus area isotherms of a PS-b-Dextran monolayer, time-dependent hysteresis was observed upon compression and

(Quasi-) 2D Aggregation of Polystyrene-b-Dextran at the Air-Water Interface

NARCIS (Netherlands)

Bosker, Wouter T. E.; Stuart, Martien A. Cohen; Norde, Willem

2013-01-01

Polystyrene-b-dextran (PS-b-Dextran) copolymers can be used to prepare dextran brushes at solid surfaces, applying Langmuir Blodgett deposition. When recording the interfacial pressure versus area isotherms of a PS-b-Dextran monolayer, time-dependent hysteresis was observed upon compression and

Nucleation of the lamellar phase from the disordered phase of the renormalized Landau-Brazovskii model

Science.gov (United States)

Carilli, Michael F.; Delaney, Kris T.; Fredrickson, Glenn H.

2018-02-01

Using the zero-temperature string method, we investigate nucleation of a stable lamellar phase from a metastable disordered phase of the renormalized Landau-Brazovskii model at parameters explicitly connected to those of an experimentally accessible diblock copolymer melt. We find anisotropic critical nuclei in qualitative agreement with previous experimental and analytic predictions; we also find good quantitative agreement with the predictions of a single-mode analysis. We conduct a thorough search for critical nuclei containing various predicted and experimentally observed defect structures. The predictions of the renormalized model are assessed by simulating the bare Landau-Brazovskii model with fluctuations. We find that the renormalized model makes reasonable predictions for several important quantities, including the order-disorder transition (ODT). However, the critical nucleus size depends sharply on proximity to the ODT, so even small errors in the ODT predicted by the renormalized model lead to large errors in the predicted critical nucleus size. We conclude that the renormalized model is a poor tool to study nucleation in the fluctuating Landau-Brazovskii model, and recommend that future studies work with the fluctuating bare model directly, using well-chosen collective variables to investigate kinetic pathways in the disorder → lamellar transition.

Oriented Structure of Pentablock Copolymers Induced by Solution Extrusion

Science.gov (United States)

Harada, Tamotsu; Bates, Frank S.; Lodge, Timothy P.

2002-03-01

Highly oriented structure of a poly(styrene-co-butadiene) pentablock copolymer (Mw; 104,700 g/mol, weight percentage of polybutadiene blocks; 29 wt of concentrated solutions. The pentablock copolymer was dissolved into mixtures of toluene and heptane, and the polymer concentration ranged from 40 wt extrusion, the pentablock copolymer was solidified either by coagulation in methanol or by evaporation of the solvent. Interestingly, a highly oriented lamellar structure was confirmed through the small angle X-ray scattering over a specific range of heptane composition, which is a good solvent for polybutadiene, although the hexagonal cylinder morphology was identified for the melt sample. The transition from the oriented lamellar to highly oriented cylinder structure was observed by annealing the samples at temperatures above the glass transition temperature of polystyrene. Moreover, a transition from parallel to perpendicular orientation in the lamellar state was observed with an increase of the extrusion shear rate. A comparison between pentablock and triblock copolymers will be also discussed.

Design and Preparation of Cross-Linked Polystyrene Nanoparticles for Elastomer Reinforcement

Directory of Open Access Journals (Sweden)

Ming Lu

2010-01-01

Full Text Available Cross-linked polystyrene (PS particles in a latex form were synthesized by free radical emulsion polymerization. The nano-PS-filled elastomer composites were prepared by the energy-saving latex compounding method. Results showed that the PS particles took a spherical shape in the size of 40–60 nm with a narrow size distribution, and the glass-transition temperature of the PS nanoparticles increased with the cross-linking density. The outcomes from the mechanical properties demonstrated that when filled into styrene-butadiene rubber (SBR, nitrile-butadiene rubber (NBR, and natural rubber (NR, the cross-linked PS nano-particles exhibited excellent reinforcing capabilities in all the three matrices, and the best in the SBR matrix. In comparison with that of the carbon black filled composites, another distinguished advantage of the cross-linked PS particles filled elastomer composites was found to be light weight in density, which could help to save tremendous amount of energy when put into end products.

Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

KAUST Repository

Peinemann, Klaus-Viktor; Karunakaran, Madhavan

2015-01-01

Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

Polystyrene-b-polyethylene oxide block copolymer membranes, methods of making, and methods of use

KAUST Repository

Peinemann, Klaus-Viktor

2015-04-16

Embodiments of the present disclosure provide for polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer nanoporous membranes, methods of making a PS-b-PEO block copolymer nanoporous membrane, methods of using PS-b-PEO block copolymer nanoporous membranes, and the like.

Analysis of acrylonitrile, 1,3-butadiene, and related compounds in acrylonitrile-butadiene-styrene copolymers for kitchen utensils and children's toys by headspace gas chromatography/mass spectrometry.

Science.gov (United States)

Ohno, Hiroyuki; Kawamura, Yoko

2010-01-01

A headspace gas chromatography/mass spectrometry method was developed for the simultaneous determination of the residual levels of acrylonitrile (AN), 1,3-butadiene (1,3-BD), and their related compounds containing propionitrile (PN) and 4-vinyl-1-cyclohexene (4-VC) in acrylonitrile-butadiene-styrene (ABS) copolymers for kitchen utensils and children's toys. A sample was cut into small pieces, then N,N-dimethylacetamide and an internal standard were added in a sealed headspace vial. The vial was incubated for 1 h at 90 degrees C and the headspace gas was analyzed by gas chromatography/mass spectrometry. The recovery rates of the analytes were 93.3-101.8% and the coefficients of variation were 0.3-6.5%. In ABS copolymers, the levels were 0.3-50.4 microg/g for AN, ND-4.5 microg/g for PN, 0.06-1.58 microg/g for 1,3-BD, and 1.1-295 microg/g for 4-VC. The highest level was found for 4-VC, which is a dimer of 1,3-BD, and the next highest was for AN, which is one of the monomers of the ABS copolymer. Furthermore, the method was also applied to acrylonitrile-styrene (AS) copolymers and polystyrenes (PS) for kitchen utensils, and nitrile-butadiene rubber (NBR) gloves. In AS copolymers, AN and PN were detected at 16.8-54.5 and 0.8-6.9 microg/g, respectively. On the other hand, the levels in PS and NBR samples were all low.

Photo-Induced Micellization of Block Copolymers

Directory of Open Access Journals (Sweden)

Satoshi Kuwayama

2010-11-01

Full Text Available We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene-block-polystyrene diblock copolymer (PBSt-b-PSt. BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp in the presence of photo-acid generators, such as bis(alkylphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium triflate. The 1H NMR analysis confirmed that PBSt-b-PSt was converted into poly(4-vinylphenol-block-PSt by the irradiation, resulting in self-assembly into micelles. The irradiation in the presence of the photo-acid generator also induced the micellization of poly(4-pyridinemethoxymethylstyrene-block-polystyrene diblock copolymer (PPySt-b-PSt. Micellization occurred by electron transfer from the pyridine to the photo-acid generator in their excited states and provided monodispersed spherical micelles with cores of PPySt blocks. Further, the photo-Claisen rearrangement caused the micellization of poly(4-allyloxystyrene-block-polystyrene diblock copolymer (PASt-b-PSt. Micellization was promoted in cyclohexane at room temperature without a catalyst. During micellization, the elimination of the allyl groups competitively occurred along with the photorearrangement of the 4-allyloxystyrene units into the 3-allyl-4-hydroxystyrene units.

Dielectric study of Poly(styrene- co -butadiene) Composites with Carbon Black, Silica, and Nanoclay

KAUST Repository

Vo, Loan T.

2011-08-09

Dielectric spectroscopy is used to measure polymer relaxation in styrene-butadiene rubber (SBR) composites. In addition to the bulk polymer relaxation, the SBR nanocomposites also exhibit a slower relaxation attributed to polymer relaxation at the polymer-nanoparticle interface. The glass transition temperature associated with the slower relaxation is used as a way to quantify the interaction strength between the polymer and the surface. Comparisons were made among composites containing nanoclay, silica, and carbon black. The interfacial relaxation glass transition temperature of SBR-clay nanocomposites is more than 80 °C higher than the SBR bulk glass transition temperature. An interfacial mode was also observed for SBR-silica nanocomposites, but the interfacial glass transition temperature of SBR-silica nanocomposite is somewhat lower than that of clay nanocomposites. An interfacial mode is also seen in the carbon black filled system, but the signal is too weak to analyze quantitatively. The interfacial polymer relaxation in SBR-clay nanocomposites is stronger compared to both SBR-carbon black and SBR-silica composites indicating a stronger interfacial interaction in the nanocomposites containing clay. These results are consistent with dynamic shear rheology and dynamic mechanical analysis measurements showing a more pronounced reinforcement for the clay nanocomposites. Comparisons were also made among clay nanocomposites using different SBRs of varying styrene concentration and architecture. The interfacial glass transition temperature of SBR-clay nanocomposites increases as the amount of styrene in SBR increases indicating that styrene interacts more strongly than butadiene with clay. © 2011 American Chemical Society.

Isotropic Lifshitz behavior in block copolymer-homopolymer blends

DEFF Research Database (Denmark)

Bates, F.S.; Maurer, W.; Lodge, T.P.

1995-01-01

A series of mixtures composed of a symmetric A-B diblock copolymer and a symmetric blend of A and B homopolymers was investigated by small-angle neutron scattering. Mean-field theory predicts that a line of lamellar-disorder transitions with wave-vector instability q* > 0 will meet a line of crit...

Synthesis and immobilization of polystyreneb-polyvinyltriethoxysilane micelles

KAUST Repository

Zhu, Saisai; Zhu, Hui; Xia, Ru; Feng, Xiaoshuang; Chen, Peng; Qian, Jiasheng; Cao, Ming; Yang, Bin; Miao, Jibin; Su, Lifen; Song, Changjiang

2018-01-01

Diblock copolymers polystyrene-block-polyvinyltriethoxysilane (PS-b-PVTES) were synthesized via atom transfer radical polymerization (ATRP), which self-assembled into spherical micelles in solvent of THF-methanol mixtures. The self

Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

Directory of Open Access Journals (Sweden)

2008-03-01

Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

Surface morphology of PS-PDMS diblock copolymer films

DEFF Research Database (Denmark)

Andersen, T.H.; Tougaard, S.; Larsen, N.B.

2001-01-01

Spin coated thin films (∼400 Å) of poly(styrene)–poly(dimethylsiloxane) (PS–PDMS) diblock copolymers have been investigated using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. Surface segregation of the poly(dimethylsiloxane) blocks was studied for five diblock copolymers which ra...

Trillions of quantum dots, fingerprints, nanolithography with diblock copolymers and annealing of striped phases

International Nuclear Information System (INIS)

Chaikin, Paul

2003-01-01

Full text: We have been using diblock copolymers as a new way to make ultradense patterns which cover wide areas on a variety of inorganic substrates. The feature sizes are determined by the length of the polymers and can range from ∼ 5 to 50 nm. The diblock copolymers form lamellar, cylindrical (hexagonal cross-section), and spherical (BCC) phases in bulk. We use monolayer films to make templates to transfer these patterns to metals, semiconductors etc. For example we cover a three inch wafer with ∼ 3 trillion posts, holes, etc. spaced by ∼ 25nm, to make quantum dots (for semiconductor lasers), metal particles and other structures. In trying to understand how the polymer patterns order we have used atomic force microscopy (AFM) to image the cylindrical phase which lies flat on a substrate. The patterns look like fingerprints and Benard rolls and the coarsening (annealing) law we observe is t (1/4) as in previous studies of these striped phases. This law remained unexplained for decades. However, we made time lapse AFM movies which show that the annealing dynamics is governed by the attraction of disclination PAIRS, quadrupoles, rather than simple +/- annihilation. This directly provides an explanation for the alignment of the striped patterns as a function of time. Thus these systems, while aimed at technological and fundamental electronic applications are also ideal materials for studying the dynamics of ordering. Recently we have also studied the thermodynamics and kinetics of the monolayer hexatic phase and used shear strain to macroscopically align the cylindrical and hexagonal patterns. (author)

40 CFR 80.55 - Measurement methods for benzene and 1,3-butadiene.

Science.gov (United States)

2010-07-01

... accomplished by bag sampling as used for total hydrocarbons determination. This procedure is detailed in 40 CFR 86.109. (b) Benzene and 1,3-butadiene must be analyzed by gas chromatography. Expected values for benzene and 1,3-butadiene in bag samples for the baseline fuel are 4.0 ppm and 0.30 ppm respectively. At...

Ternary and quaternary nanocomposites based on polystyrene, SBS, organically modified clay and silicone-polyether

International Nuclear Information System (INIS)

Kaneko, Manuela L.Q.A.; Lourenco, Emerson; Paiva, Raphael E.F.; Felisberti, Maria I.; Yoshida, Inez V.P.

2009-01-01

This work aims the study of toughened nanocomposites based on polystyrene (PS), poly(styrene-b-butadiene-b-styrene) (SBS), organically modified clay (C20A) and silicone-polyether, PDMS-POE. The intercalation of the copolymer PDMS-POE into the clay galleries increased the interlamellar distance, improving the exfoliation of the clay during the extrusion process of the materials. C20A/PDMS-POE nanocomposite, MC20A, was prepared by mechanical mixture using 1:1 wt% ratio. MC20A was incorporated into PS and PS/SBS blends using an extruder. The materials were characterized by X-ray diffraction and stress-strain mechanical tests. MC20A/PS/SBS, prepared by extrusion, showed an increase in the interlamellar distance, suggesting the intercalation of PS or SBS into the clay galleries. The PDMSPOE acted as a 'plasticizer' for PS and PS/SBS blend. However, this effect was not reverted by the clay addition. On the contrary, the 'plasticizer' effect was intensified by the clay maybe due to the slip characteristics of PDMS-POE associated with the lamella orientation. (author)

Novel poly(ethylene oxide monomethyl ether)-b-poly(.epsilon.-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage

Czech Academy of Sciences Publication Activity Database

Petrova, Svetlana; Jäger, Eliezer; Konefal, Rafal; Jäger, Alessandro; Venturini, Cristina Garcia; Spěváček, Jiří; Pavlova, Ewa; Štěpánek, Petr

2014-01-01

Roč. 5, č. 12 (2014), s. 3884-3893 ISSN 1759-9954 R&D Projects: GA ČR GAP208/10/1600; GA TA ČR TE01020118 Institutional support: RVO:61389013 Keywords : MPOE-b-PCL diblock copolymers * ring-opening polymerization * "click" chemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.520, year: 2014

Neutral, anionic, cationic, and zwitterionic diblock copolymers featuring poly(2-methoxyethyl acrylate) hydrophobic segments

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Jankova Atanasova, Katja; Hvilsted, Søren

2013-01-01

-b-PDMAEMA while the betainisation of the latter provides zwitterionic diblock amphiphile PMEA-b-PDMAPS. Inspection of these macromolecular architectures by NMR spectroscopy and size exclusion chromatography (SEC) confirms a fairly high degree of control over the reactions emphasizing flexibility and precision...

Directed Self-Assembly of Diblock Copolymer Thin Films on Prepatterned Metal Nanoarrays.

Science.gov (United States)

Chang, Tongxin; Huang, Haiying; He, Tianbai

2016-01-01

The sequential layer by layer self-assembly of block copolymer (BCP) nanopatterns is an effective approach to construct 3D nanostructures. Here large-scale highly ordered metal nano-arrays prepared from solvent annealed thin films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer are used to direct the assembly of the same BCP. The influence of initial loading concentration of metal precursor, the type of metal nanoparticle (gold, platinum, and silver), and the nanoparticle-substrate interaction on the directed assembly behavior of the upper BCP layer have been focused. It is found that the upper BCP film can be completely directed by the gold nanoarray with P2VP domain exclusively located between two adjacent gold nanowires or nanodots, which behaves the same way as on the platinum nanoarray. While the silver nanoarray can be destroyed during the upper BCP self-assembly with the silver nanoparticles assembled into the P2VP domain. Based on the discussions of the surface energy of nanoparticles and the interplay between nanoparticle-substrate interaction and nanoparticle-polymer interaction, it is concluded that the effect of immobilization of nanoparticles on the substrate, together with entropy effect to minimize the energetically unfavorable chain stretching contributes to the most effective alignment between each layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442

DEFF Research Database (Denmark)

Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun

2012-01-01

), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature...... (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. CONCLUSIONS: It is possible to produce PHA......BACKGROUND: Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB...

New techniques in lamellar keratoplasty.

Science.gov (United States)

Alio, Jorge L; Shah, Sunil; Barraquer, Carmen; Bilgihan, Kamil; Anwar, Mohammed; Melles, Gerrit R J

2002-08-01

In the past years, several lamellar keratoplasty surgical techniques have been developed, modified or improved in the past years, including microkeratome assisted anterior and posterior lamellar keratoplasty, anterior lamellar keratoplasty using air-dissection or visco-dissection, sutureless posterior lamellar keratoplasty, LASIK for postkeratoplasty astigmatism, and excimer laser assisted keratophakia for keratoconus or to manage complications after LASIK. These procedures may continue to gain interest as alternative procedures for a penetrating keratoplasty in the treatment of various corneal disorders.

Effect of casting solvents on the properties of styrene-butadiene-styrene block copolymers studied by positron annihilation techniques

International Nuclear Information System (INIS)

Djermouni, B.; Ache, H.J.

1980-01-01

The positron annihilation technique was used to study the properties of styrene-butadiene-styrene block copolymers obtained by casting them in four different solvents: toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone. The positron annihilation rates plotted as a function of temperature show in all films irregularities at -70 and +85 0 C which were attributed to the onset of motions in the polybutadiene and polystyrene domaines, respectively. In addition to that, two irregularities were observed at -14 and +10 0 C if a poor solvent, such as ethyl acetate or methyl ethyl ketone, was used, while films cast in a good solvent such as toluene or carbon tetrachloride show only one additional irregularity on the lambda 2 -T curves at -14 0 C. The latter results were explained in terms of the interfacial model by assuming that these irregularities correspond to the glass transition of interlayer phases between the pure polystyrene and the pure polybutadiene phases. The one which shows the irregularity at -14 0 C could be the phase in which polybutadiene is the major component, while the transition at +10 0 C can be attributed to a phase in which polystyrene is the dominating factor

Supramolecular Assemblies from Poly(styrene-block-poly(4-vinylpyridine Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

Directory of Open Access Journals (Sweden)

Jean-François Gohy

2013-06-01

Full Text Available Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA, with poly(styrene-block-poly(4-vinylpyridine (PS-b-P4VP diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine (P4VP blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.

Coupling of microphase separation and dewetting in weakly segregated diblock co-polymer ultrathin films.

Science.gov (United States)

Yan, Derong; Huang, Haiying; He, Tianbai; Zhang, Fajun

2011-10-04

We have studied the coupling behavior of microphase separation and autophobic dewetting in weakly segregated poly(ε-caprolactone)-block-poly(L-lactide) (PCL-b-PLLA) diblock co-polymer ultrathin films on carbon-coated mica substrates. At temperatures higher than the melting point of the PLLA block, the co-polymer forms a lamellar structure in bulk with a long period of L ∼ 20 nm, as determined using small-angle X-ray scattering. The relaxation procedure of ultrathin films with an initial film thickness of h = 10 nm during annealing has been followed by atomic force microscopy (AFM). In the experimental temperature range (100-140 °C), the co-polymer dewets to an ultrathin film of itself at about 5 nm because of the strong attraction of both blocks with the substrate. Moreover, the dewetting velocity increases with decreasing annealing temperatures. This novel dewetting kinetics can be explained by a competition effect of the composition fluctuation driven by the microphase separation with the dominated dewetting process during the early stage of the annealing process. While dewetting dominates the relaxation procedure and leads to the rupture of the ultrathin films, the composition fluctuation induced by the microphase separation attempts to stabilize them because of the matching of h to the long period (h ∼ 1/2L). The temperature dependence of these two processes leads to this novel relaxation kinetics of co-polymer thin films. © 2011 American Chemical Society

A comparison study of rhodamine B photodegradation over nitrogen-doped lamellar niobic acid and titanic acid under visible-light irradiation.

Science.gov (United States)

Li, Xiukai; Kikugawa, Naoki; Ye, Jinhua

2009-01-01

A solid-state reaction method with urea as a nitrogen precursor was used to prepare nitrogen-doped lamellar niobic and titanic solid acids (i.e., HNb(3)O(8) and H(2)Ti(4)O(9)) with different acidities for visible-light photocatalysis. The photocatalytic activities of the nitrogen-doped solid acids were evaluated for rhodamine B (RhB) degradation and the results were compared with those obtained over the corresponding nitrogen-doped potassium salts. Techniques such as XRD, BET, SEM, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy were adopted to explore the nature of the materials as well as the characteristics of the doped nitrogen species. It was found that the intercalation of the urea precursor helped to stabilize the layered structures of both lamellar solid acids and enabled easier nitrogen doping. The effects of urea intercalation were more significant for the more acidic HNb(3)O(8) sample than for the less acidic H(2)Ti(4)O(9). Compared with the nitrogen-doped KNb(3)O(8) and K(2)Ti(4)O(9) samples, the nitrogen-doped HNb(3)O(8) and H(2)Ti(4)O(9) solid acids absorb more visible light and exhibit a superior activity for RhB photodegradation under visible-light irradiation. The nitrogen-doped HNb(3)O(8) sample performed the best among all the samples. The results of the current study suggest that the protonic acidity of the lamellar solid-acid sample is a key factor that influences nitrogen doping and the resultant visible-light photocatalysis.

Side-chain-controlled self-assembly of polystyrene-polypeptide miktoarm star copolymers

KAUST Repository

Junnila, Susanna

2012-03-27

We show how the self-assembly of miktoarm star copolymers can be controlled by modifying the side chains of their polypeptide arms, using A 2B and A 2B 2 type polymer/polypeptide hybrids (macromolecular chimeras). Initially synthesized PS 2PBLL and PS 2PBLL 2 (PS, polystyrene; PBLL, poly(ε-tert-butyloxycarbonyl-l-lysine) ) miktoarms were first deprotected to PS 2PLLHCl and PS 2PLLHCl 2 miktoarms (PLLHCl, poly(l-lysine hydrochloride)) and then complexed ionically with sodium dodecyl sulfonate (DS) to give the supramolecular complexes PS 2PLL(DS) and PS 2(PLL(DS)) 2. The solid-state self-assemblies of these six miktoarm systems were studied by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and small- and wide-angle X-ray scattering (SAXS, WAXS). The side chains of the polypeptide arms were observed to have a large effect on the solubility, polypeptide conformation, and self-assembly of the miktoarms. Three main categories were observed: (i) lamellar self-assemblies at the block copolymer length scale with packed layers of α-helices in PS 2PBLL and PS 2PBLL 2; (ii) charge-clustered polypeptide micelles with less-defined conformations in a nonordered lattice within a PS matrix in PS 2PLLHCl and PS 2PLLHCl 2; (iii) lamellar polypeptide-surfactant self-assemblies with β-sheet conformation in PS 2PLL(DS) and PS 2(PLL(DS)) 2 which dominate over the formation of block copolymer scale structures. Differences between the 3- and 4-arm systems illustrate how packing frustration between the coil-like PS arms and rigid polypeptide conformations can be relieved by the right number of arms, leading to differences in the extent of order. © 2012 American Chemical Society.

Assessment of lamellar tearing

International Nuclear Information System (INIS)

McEnerney, J.W.

1978-03-01

Information on lamellar tearing is summarized and related to proposed ASME Code requirements. Lamellar tearing is characterized as a complex phenomenon related to poor short transverse ductility and through-thickness strain. The material, welding, and design variables that affect lamellar tearing are shown to be complex and interrelated. The commonly reported tests for assessing material susceptibility are described, with the controversy over their validity being carefully detailed. Although the use of a nondestructive test such as ultrasonic examination is most desirable, a widely applicable test method does not appear to be available. Of the destructive tests, the short transverse tensile reduction-of-area currently offers the most applicable means of assessing material susceptibility. However, because of the importance of matrix toughness, the short transverse Charpy V-notch test should be considered for use as an additional test if acceptance limits are developed. The ultrasonic detection of lamellar tears is susceptible to interpretation errors, which can make it overly conservative and lead to unnecessary repairs. The repair of tears is described as costly, difficult, and sometimes ineffective. Current design requirements appear to preclude any failures during static and fatigue service loads. However, without improvement of short transverse ductility, certain dynamic service loads could cause lamellar tearing failures. Two alternate design paths are recommended to prevent tearing during fabrication or service loading. The current and proposed ASME requirements dealing with lamellar tearing are reviewed and recommendations are made

Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles

Science.gov (United States)

Greene, Anna C.; Zhu, Jiahua; Pochan, Darrin J.; Jia, Xinqiao; Kiick, Kristi L.

2011-01-01

In order to expand the utility of current polymeric micellar systems, we have developed amphiphilic multiblock copolymers containing alternating blocks of poly(acrylic acid) and poly(styrene). Heterotelechelic poly(tert-butyl acrylate-b-styrene) diblock copolymers containing an α-alkyne and an ω-azide were synthesized by atom transfer radical polymerization (ATRP), allowing control over the molecular weight while maintaining narrow polydispersity indices. The multiblock copolymers were constructed by copper-catalyzed azide-alkyne cycloaddition of azide-alkyne end functional diblock copolymers which were then characterized by 1H NMR, FT-IR and SEC. The tert-butyl moieties of the poly(tert-butyl acrylate-b-styrene) multiblock copolymers were easily removed to form the poly(acrylic acid-b-styrene) multiblock copolymer ((PAA-PS)9), which contained up to 9 diblock repeats. The amphiphilic multiblock (PAA-PS)9 (Mn = 73.3 kg/mol) was self-assembled by dissolution into tetrahydrofuran and extensive dialysis against deionized water for 4 days. The critical micelle concentration (CMC) for (PAA-PS)9 was determined by fluorescence spectroscopy using pyrene as a fluorescent probe and was found to be very low at 2 × 10-4 mg/mL. The (PAA-PS)9 multiblock was also analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter of the particles was found to be 11 nm. Discrete spherical particles were observed by TEM with an average particle diameter of 14 nm. The poly(acrylic acid) periphery of the spherical particles should allow for future conjugation of biomolecules. PMID:21552373

Structural Transformation of Diblock Copolymer/Homopolymer Assemblies by Tuning Cylindrical Confinement and Interfacial Interactions.

Science.gov (United States)

Xu, Jiangping; Wang, Ke; Liang, Ruijing; Yang, Yi; Zhou, Huamin; Xie, Xiaolin; Zhu, Jintao

2015-11-17

In this study, we report the controllable structural transformation of block copolymer/homopolymer binary blends in cylindrical nanopores. Polystyrene-b-poly(4-vinylpyridine)/homopolystyrene (SVP/hPS) nanorods (NRs) can be fabricated by pouring the polymers into an anodic aluminum oxide (AAO) channel and isolated by selective removal of the AAO membrane. In this two-dimensional (2D) confinement, SVP self-assembles into NRs with concentric lamellar structure, and the internal structure can be tailored with the addition of hPS. We show that the weight fraction and molecular weight of hPS and the diameter of the channels can significantly affect the internal structure of the NRs. Moreover, mesoporous materials with tunable pore shape, size, and packing style can be prepared by selective solvent swelling of the structured NRs. In addition, these NRs can transform into spherical structures through solvent-absorption annealing, triggering the conversion from 2D to 3D confinement. More importantly, the transformation dynamics can be tuned by varying the preference property of surfactant to the polymers. It is proven that the shape and internal structure of the polymer particles are dominated by the interfacial interactions governed by the surfactants.

Polyanionic pH-responsive polystyrene-b-poly(4-vinyl pyridine-N-oxide) isoporous membranes

KAUST Repository

Shevate, Rahul

2015-12-01

Recently isoporous block copolymer (BCP) membranes obtained by non-solvent induced phase separation gained a lot of attention due to their highly ordered surface layer, high flux and superior separation properties. These polystyrene-b-poly-4-vinylpyridine (PS-b-P4VP) based membranes showed a strong flux dependence of pH; pores closed at low pH and opened at high pH. The pH-response could now be reversed by a simple post modification; pores are now opening at low pH and closing at high pH. The original membrane was transformed into a polyanionic pH responsive membrane in a one step chemical modification without affecting the isoporous surface morphology. A polystyrene-b-poly-4-vinylpyridine-N-oxide (PS-b-P4VPN-oxide) membrane is obtained by selective oxidation of the PS-b-P4VP membrane. The in situ generated peracid obtained by reacting acetic acid and hydrogen peroxide is employed for oxidation. Surprisingly not only the asymmetric membrane structure with the isoporous skin was retained, but also the mechanical and chemical membrane stability was improved significantly. The modified membranes are insoluble in solvents like DMF, NMP and DMSO. Two kinds of PS-b-P4VP based isoporous membranes are available now with reverse flux response to pH. This opens the door to new interesting charge based fractionations.

Tunable Photonic Band Gap of PS-b-P2VP Lamellar Film Using Metal Ions and pH Gradation.

Science.gov (United States)

Baek, Young-Bin; Choi, Soo-Hyung; Shin, Dong-Myung

2015-02-01

Optical properties of photonic crystal film were investigated by tuning photonic band gap (PBG). The lamellar-forming photonic films were prepared by nearly symmetric poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) block copolymers. Molecular weight of PS block and P2VP block is 52 kg/mol, and 57 kg/mol, respectively. When submerged in water, the lamellar films were swollen and show Bragg reflection in visible light region. We observed that the reflection color can be tuned by ion concentration (e.g., hydrogen or metal ion) in water. The higher concentration of hydrogen ion in solution, the longer reflectance wavelength shifted (from 537 nm to 743 nm). In addition, max-reflectance wavelength is dependent on both metal ion and the concentration. The max-reflectance wavelength is shifted from 653 nm (i.e., in water without ion) to 430 nm, 465 nm, and 505 nm for 120 mM of Ca2+, Fe2+, and Cu2+, respectively. Therefore, we can control the photonic band gap of photonic devices by changing the condition of swelling solution.

Improvement of radiation resistance of polypropylene by blending with polyethylene and polystyrene

International Nuclear Information System (INIS)

Al Aji, Z.

2001-01-01

The use of polypropylene in production of medical component and packaging materials makes it an interesting material for applied research. Since the use of ethylene oxide for sterilization of medical components will be forbidden in the next future because of its carcinogens effect. Therefore, another alternative sterilization methods are required. The use of Gamma radiation is already established for sterilization of some medical components, this technique causes change in the physical mechanical properties of polypropylene, which makes the addition of stabilizers necessary. In this work, blends of domestically used polymers, polypropylene, linear low-density polyethylene, and polystyrene/butadiene were prepared in order to improve the radiation resistance of polypropylene; naphthalene was also used as an additive

SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

Institute of Scientific and Technical Information of China (English)

Huai-chao Wang; Ming-zu Zhang; Pei-hong Ni; Jin-lin He; Ying Hao; Yi-xian Wu

2013-01-01

Two pH-responsive amphiphilic diblock copolymers,namely polyisobutylene-block-poly[2-(N,N-dimethylamino)ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA),were synthesized via oxyanion-initiated polymerization,and their multiple self-assembly behaviors have been studied.An exo-o1efin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end,and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K+).PIB-O-K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer,resulting in a cationic diblock copolymer PIB-b-PDMAEMA.With the similar synthesis procedure,the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block.The functional PIB and block copolymers have been fully characterized by 1H-NMR,FT-IR spectroscopy,and gel permeation chromatography (GPC).These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent.Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles,vesicles with different particle sizes and cylindrical aggregates,depending on various factors including block copolymer composition,solvent polarity and pH value.

The effect of long-term oxidation on the rheological properties of polymer modified asphalts

Energy Technology Data Exchange (ETDEWEB)

Yonghong Ruan; Richard R. Davison; Charles J. Glover [Texas A & M University, College Station, TX (United States). Department of Chemical Engineering

2003-10-01

The effect of long-term aging on rheological properties of polymer modified asphalt binders was studied. Modifiers included diblock poly(styrene-b-butadiene) rubber, triblock poly(styrene-b-butadiene-b-styrene), and tire rubber. Asphalt aging was carried out either at 60{sup o}C in a controlled environmental room or at 100{sup o}C in a pressure aging vessel (AASHTO Provisional Standards, 1993). Both dynamic shear properties and extensional properties were investigated. Polymer modification resulted in increased asphalt complex modulus at high temperatures, decreased asphalt complex modulus at low temperatures, broadened relaxation spectra, and improved ductility. Oxidative aging decreased asphalt temperature susceptibility, damaged the polymer network in binders, further broadened the relaxation spectrum, and diminished polymer effectiveness in improving asphalt ductility. 27 refs., 8 figs., 3 tabs.

Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

KAUST Repository

Misichronis, Konstantinos

2017-03-15

A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (TODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χeff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. These copolymers exhibit well-ordered structures even at high temperatures (∼260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.

Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

KAUST Repository

Misichronis, Konstantinos; Chen, Jihua; Imel, Adam; Kumar, Rajeev; Thostenson, James; Hong, Kunlun; Dadmun, Mark; Sumpter, Bobby G.; Kennemur, Justin G.; Hadjichristidis, Nikolaos; Mays, Jimmy W.; Avgeropoulos, Apostolos

2017-01-01

A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (TODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χeff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. These copolymers exhibit well-ordered structures even at high temperatures (∼260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.

Pattern interpolation in thin films of lamellar, symmetric copolymers on nano-patterned substrates

Science.gov (United States)

Detcheverry, Francois; Nagpal, Umang; Liu, Guoliang; Nealey, Paul; de Pablo, Juan

2009-03-01

A molecular model of block copolymer systems is used to conduct a systematic study of the morphologies that arise when thin films of symmetric, lamellar forming block copolymer materials are deposited on nanopatterned surfaces. Over 500 distinct cases are considered. It is found that, in general, three distinct morphologies can arise depending on the strength of the substrate-polymer interactions, the film thickness, and the period of the substrate pattern. The relative stability of those morphologies is determined by direct calculation of the free energy differences. The dynamic propensity of those morphologies to emerge is examined by careful analysis of simulated trajectories. The results of this systematic study are used to interpret recent experimental data for films of polystyrene-PMMA copolymers on chemically nanopatterned surfaces.

Poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers: synthesis, self-assembly and interaction

NARCIS (Netherlands)

Hofman, Anton H.; Alberda van Ekenstein, Gerhard; Woortman, Albert; ten Brinke, Gerrit; Loos, Katja

2015-01-01

Controlled radical polymerization of 4-vinylpyridine (4VP) and N-acryloylpiperidine (API) by the RAFT process allowed preparation of well-defined double hydrogen bond accepting P4VP-b-PAPI diblock copolymers. The miscibility of this new monomer pair was studied via a random copolymer blend approach

Proton conducting sulphonated fluorinated poly(styrene) crosslinked electrolyte membranes

Energy Technology Data Exchange (ETDEWEB)

Soules, A.; Ameduri, B.; Boutevin, B.; David, G. [Institut Charles Gerhardt UMR CNRS 5253 Equipe, Ingenierie et Architectures Macromoleculaires,' ' Ecole Nationale Superieure de Chimie de Montpellier, 8 rue de l' Ecole Normale, 34296 Montpellier, Cedex 05 (France); Perrin, R. [CEA Le Ripault Departement des Materiaux, DMAT/SCMF/LSTP, BP16 - 37260 Monts (France); Gebel, G. [Structure et Proprietes des Architectures Moleculaires UMR 5819 (CEA-CNRS-UJF), INAC, SPrAM, CEA Grenoble, 17 Rue des Martyrs, 38054 Grenoble, Cedex 9 (France)

2011-10-15

Potential membranes for polymer electrolyte membrane fuel cell based on crosslinked sulphonated fluorinated polystyrenes (PS) were synthesised in two steps. First, azide-telechelic polystyrene was obtained by iodine transfer polymerisation of styrene in the presence of 1,6-diiodoperfluorohexane followed by azido chain-end functionalisation. Then azide-telechelic polystyrene was efficiently crosslinked with 1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane under UV irradiation. After 45 min only, almost completion of azide crosslinking could be achieved, resulting in crosslinked membranes with insoluble fractions higher than 95%. The sulphonation of the crosslinked membranes afforded ionic exchange capacities (IECs) ranging from 2.2 to 3.2 meq g{sup -1}. The hydration number was shown to be very high (from 30 to 75), depending on both the content of perfluorodecane and of sulphonic acid groups. The morphology of the membranes, assessed by small-angle X-ray scattering, was found to be a lamellar-type structure with two types of ionic domains. For the membrane that exhibited an IEC value of 2.2 meq.g{sup -1}, proton conductivity was in the same range as that of Nafion {sup registered} (120-135 mS.cm{sup -1}), whereas the membrane IEC value of 3.2 meq.g{sup -1} showed a proton conductivity higher than that of Nafion {sup registered} in liquid water from 25 to 80 C, though a high water uptake. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Trilayered Morphology of an ABC Triple Crystalline Triblock Terpolymer

KAUST Repository

Palacios, Jordana K.

2017-09-07

Triple crystalline triblock terpolymers are materials with remarkable semicrystalline superstructures. In this work, we report for first time the alternating triple lamellar morphology that self-assembles inside spherulites of a triblock terpolymer composed of poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA). The morphology of the PEO-b-PCL-b-PLLA triblock terpolymer is compared to an analogous PCL-b-PLLA diblock copolymer. Both diblock and triblock form a single phase in the melt. Two crystallization protocols were employed to create particular crystalline morphologies. In both cases, the isothermal crystallization of the PLA block is induced first (at 81 °C, a temperature above the melting points of both PCL and PEO blocks) and PLLA spherulites form a template, whereupon cooling the other two blocks can crystallize within the PLLA interlamellar spaces. WAXS analysis demonstrated the double crystalline and triple crystalline nature of the materials. The lamellar structure was evaluated by AFM observations and SAXS measurements. Moreover, theoretical SAXS curves of one-dimensional structural models were calculated. AFM micrographs of the triblock terpolymer evidenced the three different lamellae of PLLA, PCL and PEO that coexist together within the same spherulite. Three different lamellar thickness were determined, and their dimensions suggested that all blocks crystallized in chain-folded conformations. The evolution of the triple lamellar morphology during heating of tricrystalline samples was followed by in situ synchrotron SAXS measurements. The theoretical analysis of the SAXS curves of the triblock terpolymer allowed us to propose a stacking morphological model, in which a particular trilayer structure exists, where one lamella of PCL or one lamella of PEO is inserted randomly between two adjacent PLLA lamellae.

Thin Films of Novel Linear-Dendritic Diblock Copolymers

Science.gov (United States)

Iyer, Jyotsna; Hammond, Paula

1998-03-01

A series of diblock copolymers with one linear block and one dendrimeric block have been synthesized with the objective of forming ultrathin film nanoporous membranes. Polyethyleneoxide serves as the linear hydrophilic portion of the diblock copolymer. The hyperbranched dendrimeric block consists of polyamidoamine with functional end groups. Thin films of these materials made by spin casting and the Langmuir-Blodgett techniques are being studied. The effect of the polyethylene oxide block size and the number and chemical nature of the dendrimer end group on the nature and stability of the films formed willbe discussed.

Synthesis of Diblock Codendrimer by Double Click Chemistry

Energy Technology Data Exchange (ETDEWEB)

Lee, Jae Wook; Han, Seung Choul; Ji, Won Ho [Dong-A Univ., Busan (Korea, Republic of); Jin, Sungho [Pusan National Univ., Busan (Korea, Republic of); Kim, Ji Hyeon [Gachon Univ., Seongnam (Korea, Republic of)

2012-12-15

Efficient double click methods for the synthesis of diblock codendrimers were developed. The synthetic strategy involved the sequential click reactions between an alkyne and an azide. The short core building block, 1,4-diazidobutane, was chosen to serve as the azide functionalities for dendrimer growth via click reactions with the alkyne-functionalized PAMAM dendrons as hydrophilic dendron and alkyne-functionalized Frechet-type dendrons as hydrophobic dendron. The structure of diblock codendrimers was confirmed by {sup 1}H and {sup 13}C NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis.

Synthesis of Diblock Codendrimer by Double Click Chemistry

International Nuclear Information System (INIS)

Lee, Jae Wook; Han, Seung Choul; Ji, Won Ho; Jin, Sungho; Kim, Ji Hyeon

2012-01-01

Efficient double click methods for the synthesis of diblock codendrimers were developed. The synthetic strategy involved the sequential click reactions between an alkyne and an azide. The short core building block, 1,4-diazidobutane, was chosen to serve as the azide functionalities for dendrimer growth via click reactions with the alkyne-functionalized PAMAM dendrons as hydrophilic dendron and alkyne-functionalized Frechet-type dendrons as hydrophobic dendron. The structure of diblock codendrimers was confirmed by 1 H and 13 C NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis

En face spectral domain optical coherence tomography analysis of lamellar macular holes.

Science.gov (United States)

Clamp, Michael F; Wilkes, Geoff; Leis, Laura S; McDonald, H Richard; Johnson, Robert N; Jumper, J Michael; Fu, Arthur D; Cunningham, Emmett T; Stewart, Paul J; Haug, Sara J; Lujan, Brandon J

2014-07-01

To analyze the anatomical characteristics of lamellar macular holes using cross-sectional and en face spectral domain optical coherence tomography. Forty-two lamellar macular holes were retrospectively identified for analysis. The location, cross-sectional length, and area of lamellar holes were measured using B-scans and en face imaging. The presence of photoreceptor inner segment/outer segment disruption and the presence or absence of epiretinal membrane formation were recorded. Forty-two lamellar macular holes were identified. Intraretinal splitting occurred within the outer plexiform layer in 97.6% of eyes. The area of intraretinal splitting in lamellar holes did not correlate with visual acuity. Eyes with inner segment/outer segment disruption had significantly worse mean logMAR visual acuity (0.363 ± 0.169; Snellen = 20/46) than in eyes without inner segment/outer segment disruption (0.203 ± 0.124; Snellen = 20/32) (analysis of variance, P = 0.004). Epiretinal membrane was present in 34 of 42 eyes (81.0%). En face imaging allowed for consistent detection and quantification of intraretinal splitting within the outer plexiform layer in patients with lamellar macular holes, supporting the notion that an area of anatomical weakness exists within Henle's fiber layer, presumably at the synaptic connection of these fibers within the outer plexiform layer. However, the en face area of intraretinal splitting did not correlate with visual acuity, disruption of the inner segment/outer segment junction was associated with significantly worse visual acuity in patients with lamellar macular holes.

Tuning of thermally induced sol-to-gel transitions of moderately concentrated aqueous solutions of doubly thermosensitive hydrophilic diblock copolymers poly(methoxytri(ethylene glycol) acrylate)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid).

Science.gov (United States)

Jin, Naixiong; Zhang, Hao; Jin, Shi; Dadmun, Mark D; Zhao, Bin

2012-03-15

We report in this article a method to tune the sol-to-gel transitions of moderately concentrated aqueous solutions of doubly thermosensitive hydrophilic diblock copolymers that consist of two blocks exhibiting distinct lower critical solution temperatures (LCSTs) in water. A small amount of weak acid groups is statistically incorporated into the lower LCST block so that its LCST can be tuned by varying solution pH. Well-defined diblock copolymers, poly(methoxytri(ethylene glycol) acrylate)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid) (PTEGMA-b-P(DEGEA-co-AA)), were prepared by reversible addition-fragmentation chain transfer polymerization and postpolymerization modification. PTEGMA and PDEGEA are thermosensitive water-soluble polymers with LCSTs of 58 and 9 °C, respectively, in water. A 25 wt % aqueous solution of PTEGMA-b-P(DEGEA-co-AA) with a molar ratio of DEGEA to AA units of 100:5.2 at pH = 3.24 underwent multiple phase transitions upon heating, from a clear, free-flowing liquid (sol-to-gel transition temperature (T(sol-gel)) shifted to higher values, while the gel-to-sol transition (T(gel-sol)) and the clouding temperature (T(clouding)) of the sample remained essentially the same. These transitions and the tunability of T(sol-gel) originated from the thermosensitive properties of two blocks of the diblock copolymer and the pH dependence of the LCST of P(DEGEA-co-AA), which were confirmed by dynamic light scattering and differential scanning calorimetry studies. Using the vial inversion test method, we mapped out the C-shaped sol-gel phase diagrams of the diblock copolymer in aqueous buffers in the moderate concentration range at three different pH values (3.24, 5.58, and 5.82, all measured at ~0 °C). While the upper temperature boundaries overlapped, the lower temperature boundary shifted upward and the critical gelation concentration increased with the increase of pH. The AA content in PTEGMA-b-P(DEGEA-co-AA) was found to have a significant

Boron Behavior Induced Lamellar Structure and Anisotropic Magnetic Properties of Nd{sub 2}Fe{sub 14}B during HDDR process

Energy Technology Data Exchange (ETDEWEB)

Choi, Moonhee; Song, Yeonghwan [Samsung Electro-Mechanics, Suwon (Korea, Republic of); Cho, Seungchan; Jo, Ilguk; Yu, Jihun [Korea Institute of Materials Science, Changwon (Korea, Republic of); Kim, Chiho; Kim, Yangdo [Pusan National University, Busan (Korea, Republic of)

2017-08-15

The anisotropy of the Nd{sub 2}Fe{sub 14}B powder is originated during the creation of a fine Fe2B lamellar structure in the disproportionation step. The aspect ratio (A/R) of Fe2B structure increased from 3.37 ± 1.5 to 6.69 ± 3.2 during phase decomposition for 0 ∼ 60 min at 820 ℃ (P{sub H2} = 10 kPa). The Fe{sub 2}B having high A/R ratio recombined Nd{sub 2}Fe{sub 14}B, which is close to the single domain, and the magnetic properties are also improved with increasing A/R ratio.

Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442.

Science.gov (United States)

Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun; Chen, Guo-Qiang

2012-04-05

Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. It is possible to produce PHA block copolymers of various kinds using the recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. In comparison to a random copolymer poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P(HB-co-HHx)) and a blend sample of PHB and PHHx, the PHB-b-PHHx showed improved structural related mechanical properties.

Chrome-tanned leather shavings as a filler of butadiene-acrylonitrile rubber.

Science.gov (United States)

Przepiórkowska, A; Chrońska, K; Zaborski, M

2007-03-06

The noxious wastes from the tanning industry such as chrome-tanned leather shavings were used as the only filler of rubber mixes containing carboxylated butadiene-acrylonitrile rubber (XNBR) or butadiene-acrylonitrile rubber (NBR), and a dispersing agent Limanol PEV (Schill & Seilacher). The best form addition of leather powder to the rubber mixes is mixed the waste protein with zinc oxide. The leather powder added to the rubber mixes improves the mechanical properties: tensile strength (T(s)), elongation at break (epsilon(b)) and increase the cross-linking density of carboxylated XNBR and NBR rubber mixes. Satisfactory results of these studies are presented in this work.

Synthesis and characterization of a novel water-soluble cationic diblock copolymer with star conformation by ATRP

Energy Technology Data Exchange (ETDEWEB)

Li, Shuzhao [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3 (Canada); School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Xiao, Miaomiao [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3 (Canada); Zheng, Anna [School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Xiao, Huining, E-mail: hxiao@unb.ca [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3 (Canada)

2014-10-01

A water-soluble cationic diblock copolymer, CD-PAM-b-PMeDMA, was synthesized through atom transfer radical polymerization (ATRP) from a β-cyclodextrin (CD) macroinitiator with 10-active sites (10Br-β-CD). In order to reduce the cytotoxicity of the CD-PAM-b-PMeDMA, biocompatible polyacrylamide (PAM) was first introduced onto the surface of β-CD as a scaffold structure by ATRP using the 10Br-β-CD as a macroinitiator. The reaction conditions of AM were explored and optimized. The ATRP of [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride (MeDMA) was also performed to synthesize the second cationic block using the resulting CD-PAM as a macroinitiator. The resulting diblock copolymer shows an increased hydrodynamic radius in aqueous solution with a pretty low concentration compared with β-CD. In addition, it appears a near-uniform coniform after being deposited on mica ascribed to the presence of an asymmetric 10-arm structure. - Highlights: • A 10-arm diblock polymer was prepared by ATRP for the potential use as a non-viral gene delivery. • PAM was first synthesized in a controlled manner considering its biocompatibility. • The hydrodynamic radius of the copolymer in aqueous solution increase to 130 nm from 7.5 nm of CD. • The copolymer appears coniform after deposited on mica surface due to the charge attraction.

Pressure and temperature effects in homopolymer blends and diblock copolymers

DEFF Research Database (Denmark)

Frielinghaus, H.; Schwahn, D.; Mortensen, K.

1997-01-01

Thermal composition fluctuations in a homogeneous binary polymer blend and in a diblock copolymer were measured by small-angle neutron scattering as a function of temperature and pressure. The experimental data were analyzed with theoretical expressions, including the important effect of thermal...... fluctuations. Phase boundaries, the Flory-Huggins interaction parameter and the Ginzburg number were obtained. The packing of the molecules changes with pressure. Therefore, the degree of thermal fluctuation as a function of packing and temperature was studied. While in polymer blends packing leads, in some...... respects, to a universal behaviour, such behaviour is not found in diblock copolymers. It is shown that the Ginzburg number decreases with pressure sensitively in blends, while it is constant in diblock copolymers. The Ginzburg number is an estimation of the transition between the universality classes...

Monte Carlo simulation of diblock copolymer microphases by means of a 'fast' off-lattice model

DEFF Research Database (Denmark)

Besold, Gerhard; Hassager, O.; Mouritsen, Ole G.

1999-01-01

We present a mesoscopic off-lattice model for the simulation of diblock copolymer melts by Monte Carlo techniques. A single copolymer molecule is modeled as a discrete Edwards chain consisting of two blocks with vertices of type A and B, respectively. The volume interaction is formulated in terms...

Gender differences in the metabolism of 1,3-butadiene to butadiene diepoxide in Sprague-Dawley rats

Energy Technology Data Exchange (ETDEWEB)

Thornton-Manning, J.R.; Dahl, A.R.; Bechtold, W.E. [and others

1995-12-01

1,3-Butadiene (BD), a gaseous compound used in the production of rubber, is a potent carcinogen in mice and a weak carcinogen in rats. The mechanism of BD-induced carcinogenicity is thought to involve genotoxic effects of its reactive epoxide metabolites butadiene monoepoxide (BDO) and butadiene diepoxide (BDO{sub 2}). Studies in our laboratory have shown that levels of the epoxides, particularly BDO{sub 2}, are greater in mice-the more sensitive species-than rats. While both epoxides are genotoxic in a number of assays, BDO{sub 2} is mutagenic in TK6 human lymphoblastoid cells at concentrations approximately 100-fold lower than BDO. Species differences in carcinogenicity of BD have posed a dilemma to investigators deciding which animal model is most appropriate for BD risk assessment.

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

Science.gov (United States)

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.

Morphology and Surface Energy of a Si Containing Semifluorinated Di-block Copolymer Thin Films.

Science.gov (United States)

Shrestha, Umesh; Clarson, Stephen; Perahia, Dvora

2013-03-01

The structure and composition of an interface influence stability, adhesiveness and response to external stimuli of thin polymeric films. Incorporation of fluorine affects interfacial energy as well as thermal and chemical stability of the layers. The incompatibility between the fluorinated and non-fluorinated blocks induces segregation that leads to long range correlations where the tendency of the fluorine to migrate to interfaces impacts the surface tension of the films. Concurrently Si in a polymeric backbone enhances the flexibility of polymeric chains. Our previous studies of poly trifluoro propyl methyl siloxane-polystyrene thin films with SiF fraction 0.03-0.5 as a function of temperature have shown that the SiF block drives layering parallel to the surface of the diblock. Here in we report the structure and interfacial energies of SiF-PS in the plane of the films, as a function of the volume fraction of the SiF block obtained from Atomic Force microscopy and contact angle measurement studies. This work is supported by NSF DMR - 0907390

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.

Science.gov (United States)

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.

Effect of sequence dispersity on morphology of tapered diblock copolymers from molecular dynamics simulations.

Science.gov (United States)

Levine, William G; Seo, Youngmi; Brown, Jonathan R; Hall, Lisa M

2016-12-21

Tapered diblock copolymers are similar to typical AB diblock copolymers but have an added transition region between the two blocks which changes gradually in composition from pure A to pure B. This tapered region can be varied from 0% (true diblock) to 100% (gradient copolymer) of the polymer length, and this allows some control over the microphase separated domain spacing and other material properties. We perform molecular dynamics simulations of linearly tapered block copolymers with tapers of various lengths, initialized from fluids density functional theory predictions. To investigate the effect of sequence dispersity, we compare systems composed of identical polymers, whose taper has a fixed sequence that most closely approximates a linear gradient, with sequentially disperse polymers, whose sequences are created statistically to yield the appropriate ensemble average linear gradient. Especially at high segregation strength, we find clear differences in polymer conformations and microstructures between these systems. Importantly, the statistical polymers are able to find more favorable conformations given their sequence, for instance, a statistical polymer with a larger fraction of A than the median will tend towards the A lamellae. The conformations of the statistically different polymers can thus be less stretched, and these systems have higher overall density. Consequently, the lamellae formed by statistical polymers have smaller domain spacing with sharper interfaces.

Structural perfection of directionally solidified lamellar eutectics

International Nuclear Information System (INIS)

Attallah, T.; Gurzleski, J.E.

1976-01-01

The mechanisms for the formation of faults in lamellar eutectics are reviewed, and it is postulated that faults play several roles in eutectic freezing with their exact importance depending on the specific alloy system and the growth conditions. Faults are not the cause of lamellar spiralling although they are necessary for it to occur. Lamellar spiralling is found to occur only when the crystallographic orientations of the two eutectic phases lead to a growth component normal to the lamellar plane, and although some systems such as Pb-Sn normally spiral it is possible for them to achieve orientation relationships where no spiralling occurs

Performance of polyethylene based radiation grafted anion exchange membrane with polystyrene-b-poly (ethylene/butylene)-b-polystyrene based ionomer using NiCo2O4 catalyst for water electrolysis

Science.gov (United States)

Gupta, Gaurav; Scott, Keith; Mamlouk, Mohamed

2018-01-01

A soluble anion exchange ionomer with high OH- ion conductivity comparable to that of H+ conductivity of Nafion is synthesised by chloromethylation of polystyrene-b-poly (ethylene/butylene)-b-polystyrene (SEBS) and used with NiCo2O4 electro-catalyst for water electrolysis. The ionomer has an ion exchange capacity of 1.9 mmol g-1 and ionic conductivity of 0.14 S cm-2 at 50 °C. The cell voltage at 20 °C at 100 mA cm-2 is 1.77 and 1.72 V in, 0.1 and 1.0 M NaOH, respectively, for an optimum loading of 10 mg cm-2 NiCo2O4. At 10 mg cm-2 NiCo2O4 electrolyser cell performance is at least equal to or superior to that of IrO2 at 2 mg cm-2 with excellent stability over 1 h. When the catalyst is sprayed on the GDL instead of CCM, the performance is further improved to 1.65 V at 100 mA cm-2 at 60 °C & 0.1 M KOH. The limited AEM electrolyser performance when operating with deionised water in comparison to PEM and alkaline electrolyser arises from the sluggish OER in the AEM environment equivalent to pH of 11.5 and the two orders of magnitude lower HER activity with respect to acid medium combined with the high Tafel slope of 120 mV dec-1.

Polymer brushes on nanoparticles: their positioning in and influence on block copolymer morphology.

Science.gov (United States)

Kim, Bumjoon

2007-03-01

Polymers brushes grafted to the nanoparticle surface enable the precise positioning of particles within a block copolymer matrix by determining the compatibility of nanoparticles within a polymeric matrix and modifying the interfacial properties between polymers and inorganic nanoparticle. Short thiol terminated polystyrene (PS-SH), poly(2-vinylpyridine) (P2VP-SH) and PS-r-P2VP with the molecular weight (Mn) of 3 kg/mol were used to control the location of Au nanoparticles over PS-b-P2VP diblock copolymer template. We will discuss further the approach of varying the areal chain density (σ) of PS-SH brushes on the PS coated particles, which utilizes the preferential wetting of one block of a copolymer (P2VP) on the Au substrate. Such favorable interaction provides the strong binding of Au particles to the PS/P2VP interface as σ of PS chains on the Au particle decreases. We find that at σ above a certain value, the nanoparticles are segregated to the center of the PS domains while below this value they are segregated to the interface. The transition σ for PS-SH chains (Mn = 3.4 kg/mol) is 1.3 chains/nm^2 but unexpectedly scales as Mn-0.55 as Mn is varied from 1.5 to 13 kg/mol. In addition, we will discuss changes in block copolymer morphology that occur as the nanoparticle volume fraction (φ) is increased for nanoparticles that segregate to the domain center as well as those that segregate to the interface, the latter behaving as nanoparticle surfactants. Small φ of such surfactants added to lamellar diblock copolymers lead initially to a decrease in lamellar thickness, a consequence of decreasing interfacial tension, up to a critical value of φ beyond which the block copolymer adopts a bicontinuous morphology. I thank my collaborators G. H. Fredrickson, J. Bang, C. J. Hawker, and E. J. Kramer as well as funding by the MRL as UCSB from the NSF-MRSEC-Program Award DMR05-20418.

21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may be...

One-step route to the fabrication of highly porous polyaniline nanofiber films by using PS-b-PVP diblock copolymers as templates.

Science.gov (United States)

Li, Xue; Tian, Shengjun; Ping, Yang; Kim, Dong Ha; Knoll, Wolfgang

2005-10-11

We report a new method to control both the nucleation and growth of highly porous polyaniline (PANI) nanofiber films using porous poly(styrene-block-2-vinylpyridine) diblock copolymer (PS-b-P2VP) films as templates. A micellar thin film composed of P2VP spheres within a PS matrix is prepared by spin coating a PS-b-P2VP micellar solution onto substrates. The P2VP domains are swollen in a selective solvent of acetic acid, which results in the formation of pores in the block copolymer film. PANI is then deposited onto the substrates modified with such a porous film using electrochemical methods. During the deposition, the nucleation and growth of PANI occur only at the pores of the block copolymer film. After the continued growth of PANI by the electrochemical deposition, a porous PANI nanofiber film is obtained.

Updating the lamellar hypothesis of hippocampal organization

Directory of Open Access Journals (Sweden)

Robert S Sloviter

2012-12-01

Full Text Available In 1971, Andersen and colleagues proposed that excitatory activity in the entorhinal cortex propagates topographically to the dentate gyrus, and on through a trisynaptic circuit lying within transverse hippocampal slices or lamellae [Andersen, Bliss, and Skrede. 1971. Lamellar organization of hippocampal pathways. Exp Brain Res 13, 222-238]. In this way, a relatively simple structure might mediate complex functions in a manner analogous to the way independent piano keys can produce a nearly infinite variety of unique outputs. The lamellar hypothesis derives primary support from the lamellar distribution of dentate granule cell axons (the mossy fibers, which innervate dentate hilar neurons and area CA3 pyramidal cells and interneurons within the confines of a thin transverse hippocampal segment. Following the initial formulation of the lamellar hypothesis, anatomical studies revealed that unlike granule cells, hilar mossy cells, CA3 pyramidal cells, and Layer II entorhinal cells all form axonal projections that are more divergent along the longitudinal axis than the clearly lamellar mossy fiber pathway. The existence of pathways with translamellar distribution patterns has been interpreted, incorrectly in our view, as justifying outright rejection of the lamellar hypothesis [Amaral and Witter. 1989. The three-dimensional organization of the hippocampal formation: a review of anatomical data. Neuroscience 31, 571-591]. We suggest that the functional implications of longitudinally-projecting axons depend not on whether they exist, but on what they do. The observation that focal granule cell layer discharges normally inhibit, rather than excite, distant granule cells suggests that longitudinal axons in the dentate gyrus may mediate "lateral" inhibition and define lamellar function, rather than undermine it. In this review, we attempt a reconsideration of the evidence that most directly impacts the physiological concept of hippocampal lamellar

Outstanding compressive creep strength in Cr/Ir-codoped (Mo0.85Nb0.15)Si2 crystals with the unique cross-lamellar microstructure.

Science.gov (United States)

Hagihara, Koji; Ikenishi, Takaaki; Araki, Haruka; Nakano, Takayoshi

2017-06-21

A (Mo 0.85 Nb 0.15 )Si 2 crystal with an oriented, lamellar, C40/C11 b two-phase microstructure is a promising ultrahigh-temperature (UHT) structural material, but its low room-temperature fracture toughness and low high-temperature strength prevent its practical application. As a possibility to overcome these problems, we first found a development of unique "cross-lamellar microstructure", by the cooping of Cr and Ir. The cross-lamellar microstructure consists of a rod-like C11 b -phase grains that extend along a direction perpendicular to the lamellar interface in addition to the C40/C11 b fine lamellae. In this study, the effectiveness of the cross-lamellar microstructure for improving the high-temperature creep deformation property, being the most essential for UHT materials, was examined by using the oriented crystals. The creep rate significantly reduced along a loading orientation parallel to the lamellar interface. Furthermore, the degradation in creep strength for other loading orientation that is not parallel to the lamellar interface, which has been a serious problem up to now, was also suppressed. The results demonstrated that the simultaneous improvement of high-temperature creep strength and room temperature fracture toughness can be first accomplished by the development of unique cross-lamellar microstructure, which opens a potential avenue for the development of novel UHT materials as alternatives to existing Ni-based superalloys.

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

Science.gov (United States)

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.

Self-Assembly and Crystallization of Conjugated Block Copolymers

Science.gov (United States)

Davidson, Emily Catherine

This dissertation demonstrates the utility of molecular design in conjugated polymers to create diblock copolymers that robustly self-assemble in the melt and confine crystallization upon cooling. This work leverages the model conjugated polymer poly(3-(2'-ethyl)hexylthiophene) (P3EHT), which features a branched side chain, resulting in a dramatically reduced melting temperature (Tm 80°C) relative to the widely-studied poly(3-hexylthiophene) (P3HT) (Tm 200°C). This reduced melting temperature permits an accessible melt phase, without requiring that the segregation strength (chiN) be dramatically increased. Thus, diblock copolymers containing P3EHT demonstrate robust diblock copolymer self-assembly in the melt over a range of compositions and morphologies. Furthermore, confined crystallization in the case of both glassy (polystyrene (PS) matrix block) and soft (polymethylacrylate (PMA) matrix block) confinement is studied, with the finding that even in soft confinement, crystallization is constrained within the diblock microdomains. This success demonstrates the strategy of leveraging molecular design to decrease the driving force for crystallization as a means to achieving robust self-assembly and confined crystallization in conjugated block copolymers. Importantly, despite the relatively flexible nature of P3EHT in the melt, the diblock copolymer phase behavior appears to be significantly impacted by the stiffness (persistence length of 3 nm) of the P3EHT chain compared to the coupled amorphous blocks (persistence length 0.7 nm). In particular, it is shown that the synthesized morphologies are dominated by a very large composition window for lamellar geometries (favored at high P3EHT volume fractions); cylindrical geometries are favored when P3EHT is the minority fraction. This asymmetry of the composition window is attributed to impact of conformational asymmetry (the difference in chain stiffness, as opposed to shape) between conjugated and amorphous blocks

Surface dynamics of micellar diblock copolymer films

Science.gov (United States)

Song, Sanghoon; Cha, Wonsuk; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh

2011-03-01

We studied the structure and surface dynamics of poly(styrene)-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer films with micellar PDMS surrounded by PS shells. By `in-situ' high resolution synchrotron x-ray reflectivity and diffuse scattering, we obtained exact thickness, electron density and surface tension. A segregation layer near the top surface was appeared with increasing temperature Surface dynamics were measured as a function of film thickness and temperature by x-ray photon correlation spectroscopy. The best fit to relaxation time constants as a function of in-plane wavevectors were analyzed with a theory based on capillary waves with hydrodynamics with bilayer model Finally the viscosities for the top segregated layer as well as for the bottom layer are obtained at given temperatures This work was supported by National Research Foundation of Korea (R15-2008-006-01001-0), Seoul Research and Business Development Program (10816), and Sogang University Research Grant (2010).

Polybutadiene and Styrene-Butadiene rubbers for high-dose dosimetry

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Lucas N. [Instituto Federal de Educacao, Ciencia e Tecnologia de Goias-IFG,Campus Goiania, Goiania -GO (Brazil); Instituto de Pesquisas Energeticas e Nucleares -IPEN, Sao Paulo-SP (Brazil); Vieira, Silvio L. [Instituto de Fisica, Universidade Federal de Goias-UFG, Campus Samambaia, Goiania-GO (Brazil); Schimidt, Fernando [Instituto Federal de Educacao, Ciencia e Tecnologia de Goias-IFG,Campus Inhumas, Inhumas-GO (Brazil); Antonio, Patricia L.; Caldas, Linda V.E. [Instituto de Pesquisas Energeticas e Nucleares -IPEN, Sao Paulo-SP (Brazil)

2015-07-01

Polybutadiene and Styrene-Butadiene are synthetical rubbers used widely for pneumatic tires manufacturing. In this research, the dosimeter characteristics of those rubbers were studied for application in high-dose dosimetry. The rubber samples were irradiated with doses of 10 Gy up to 10 kGy, using a {sup 60}Co Gamma Cell-220 system (dose rate of 1.089 kGy/h) and their readings were taken on a Fourier Transform Infrared Spectroscopy-FTIR system (model Frontier/Perkin Elmer). The ratios of two absorbance peaks were taken for each kind of rubber spectrum, Polybutadiene (1306/1130 cm{sup -1}) and Styrene-Butadiene (1449/1306 cm{sup -1}). The ratio calculated was used as the response to the irradiation, and is not uniform across the sample. From the results, it can be concluded for both rubbers: a) the dose-response curves may be useful for high-dose dosimetry (greater than 250 Gy); b) their response for reproducibility presented standard deviations lower than 2.5%; c) the relative sensitivity was higher for Styrene-Butadiene (1.86 kGy{sup -1}) than for Polybutadiene (1.81 kGy{sup -1}), d) for doses of 10 kGy to 200 kGy, there was no variation in the dosimetric response. Both types of rubber samples showed usefulness as high-dose dosimeters. (authors)

Synthesis, characterization and self-assembly of well-defined linear heptablock quaterpolymers

KAUST Repository

Ntaras, Christos; Polymeropoulos, George; Zapsas, George; Ntetsikas, Konstantinos; Liontos, George; Karanastasis, Apostolos; Moschovas, Dimitrios; Rangou, Sofia; Stewart-Sloan, Charlotte; Hadjichristidis, Nikolaos; Thomas, Edwin L.; Avgeropoulos, Apostolos

2016-01-01

Two well-defined heptablock quaterpolymers of the ABCDCBA type [Α: polystyrene (PS), B: poly(butadiene) with ∼90% 1,4-microstructure (PB1,4), C: poly(isoprene) with ∼55% 3,4-microstructure (PI3,4) and D: poly(dimethylsiloxane) (PDMS)] were

Nanoformulation of D-α-tocopheryl polyethylene glycol 1000 succinate-b-poly(ε-caprolactone-ran-glycolide) diblock copolymer for breast cancer therapy.

Science.gov (United States)

Huang, Laiqiang; Chen, Hongbo; Zheng, Yi; Song, Xiaosong; Liu, Ranyi; Liu, Kexin; Zeng, Xiaowei; Mei, Lin

2011-10-01

The purpose of this research was to develop formulation of docetaxel-loaded biodegradable TPGS-b-(PCL-ran-PGA) nanoparticles for breast cancer chemotherapy. A novel diblock copolymer, d-α-tocopheryl polyethylene glycol 1000 succinate-b-poly(ε-caprolactone-ran-glycolide) [TPGS-b-(PCL-ran-PGA)], was synthesized from ε-caprolactone, glycolide and d-α-tocopheryl polyethylene glycol 1000 succinate by ring-opening polymerization using stannous octoate as catalyst. The obtained copolymers were characterized by (1)H NMR, GPC and TGA. The docetaxel-loaded TPGS-b-(PCL-ran-PGA) nanoparticles were prepared and characterized. The data showed that the fluorescence TPGS-b-(PCL-ran-PGA) nanoparticles could be internalized by MCF-7 cells. The TPGS-b-(PCL-ran-PGA) nanoparticles achieved significantly higher level of cytotoxicity than commercial Taxotere®. MCF-7 xenograft tumor model on SCID mice showed that docetaxel formulated in the TPGS-b-(PCL-ran-PGA) nanoparticles could effectively inhibit the growth of tumor over a longer period of time than Taxotere® at the same dose. In conclusion, the TPGS-b-(PCL-ran-PGA) copolymer could be acted as a novel and potential biologically active polymeric material for nanoformulation in breast cancer chemotherapy. This journal is © The Royal Society of Chemistry 2011

Surprising transformation of a block copolymer into a high performance polystyrene ultrafiltration membrane with a hierarchically organized pore structure

KAUST Repository

Shevate, Rahul

2018-02-08

We describe the preparation of hierarchical polystyrene nanoporous membranes with a very narrow pore size distribution and an extremely high porosity. The nanoporous structure is formed as a result of unusual degradation of the poly(4-vinyl pyridine) block from self-assembled poly(styrene)-b-poly(4-vinyl pyridine) (PS-b-P4VP) membranes through the formation of an unstable pyridinium intermediate in an alkaline medium. During this process, the confined swelling and controlled degradation produced a tunable pore size. We unequivocally confirmed the successful elimination of the P4VP block from a PS-b-P4VPVP membrane using 1D/2D NMR spectroscopy and other characterization techniques. Surprisingly, the long range ordered surface porosity was preserved even after degradation of the P4VP block from the main chain of the diblock copolymer, as revealed by SEM. Aside from a drastically improved water flux (∼67% increase) compared to the PS-b-P4VP membrane, the hydraulic permeability measurements validated pH independent behaviour of the isoporous PS membrane over a wide pH range from 3 to 10. The effect of the pore size on protein transport rate and selectivity (a) was investigated for lysozyme (Lys), bovine serum albumin (BSA) and globulin-γ (IgG). A high selectivity of 42 (Lys/IgG) and 30 (BSA/IgG) was attained, making the membranes attractive for size selective separation of biomolecules from their synthetic model mixture solutions.

Recent Breakthroughs in the Conversion of Ethanol to Butadiene

Directory of Open Access Journals (Sweden)

Guillaume Pomalaza

2016-12-01

Full Text Available 1,3-Butadiene is traditionally produced as a byproduct of ethylene production from steam crackers. What is unusual is that the alternative production route for this important commodity chemical via ethanol was developed a long time ago, before World War II. Currently, there is a renewed interest in the production of butadiene from biomass due to the general trend to replace oil in the chemical industry. This review describes the recent progress in the production of butadiene from ethanol (ETB by one or two-step process through intermediate production of acetaldehyde with an emphasis on the new catalytic systems. The different catalysts for butadiene production are compared in terms of structure-catalytic performance relationship, highlighting the key issues and requirements for future developments. The main difficulty in this process is that basic, acid and redox properties have to be combined in one single catalyst for the reactions of condensation, dehydration and hydrogenation. Magnesium and zirconium-based catalysts in the form of oxides or recently proposed silicates and zeolites promoted by metals are prevailing for butadiene synthesis with the highest selectivity of 70% at high ethanol conversion. The major challenge for further application of the process is to increase the butadiene productivity and to enhance the catalyst lifetime by suppression of coke deposition with preservation of active sites.

Relaxation processes in a lower disorder order transition diblock copolymer

International Nuclear Information System (INIS)

Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora; Hernández, Rebeca; Sprung, Michael

2015-01-01

The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T ODT , the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system

Vacuolar ATPase regulates surfactant secretion in rat alveolar type II cells by modulating lamellar body calcium.

Directory of Open Access Journals (Sweden)

Narendranath Reddy Chintagari

2010-02-01

Full Text Available Lung surfactant reduces surface tension and maintains the stability of alveoli. How surfactant is released from alveolar epithelial type II cells is not fully understood. Vacuolar ATPase (V-ATPase is the enzyme responsible for pumping H(+ into lamellar bodies and is required for the processing of surfactant proteins and the packaging of surfactant lipids. However, its role in lung surfactant secretion is unknown. Proteomic analysis revealed that vacuolar ATPase (V-ATPase dominated the alveolar type II cell lipid raft proteome. Western blotting confirmed the association of V-ATPase a1 and B1/2 subunits with lipid rafts and their enrichment in lamellar bodies. The dissipation of lamellar body pH gradient by Bafilomycin A1 (Baf A1, an inhibitor of V-ATPase, increased surfactant secretion. Baf A1-stimulated secretion was blocked by the intracellular Ca(2+ chelator, BAPTA-AM, the protein kinase C (PKC inhibitor, staurosporine, and the Ca(2+/calmodulin-dependent protein kinase II (CaMKII, KN-62. Baf A1 induced Ca(2+ release from isolated lamellar bodies. Thapsigargin reduced the Baf A1-induced secretion, indicating cross-talk between lamellar body and endoplasmic reticulum Ca(2+ pools. Stimulation of type II cells with surfactant secretagogues dissipated the pH gradient across lamellar bodies and disassembled the V-ATPase complex, indicating the physiological relevance of the V-ATPase-mediated surfactant secretion. Finally, silencing of V-ATPase a1 and B2 subunits decreased stimulated surfactant secretion, indicating that these subunits were crucial for surfactant secretion. We conclude that V-ATPase regulates surfactant secretion via an increased Ca(2+ mobilization from lamellar bodies and endoplasmic reticulum, and the activation of PKC and CaMKII. Our finding revealed a previously unrealized role of V-ATPase in surfactant secretion.

Self-diffusion investigations on a series of PEP-PDMS diblock copolymers with different morphologies by pulsed field gradient NMR

DEFF Research Database (Denmark)

Rittig, F.; Karger, J.; Papadakis, C.M.

1999-01-01

We report on temperature-dependent self-diffusion measurements of compositionally different and non-entangled poly(ethylene-co-propylene)-b-poly(dimethylsiloxane) PEP-PDMS diblock copolymers in the melt above and below the order-to-disorder transition temperature. Depending on the dimensionality...

Remote manipulation of posterior lamellar corneal grafts using a magnetic field.

Science.gov (United States)

Nahum, Yoav; Barliya, Tilda; Bahar, Irit; Livnat, Tami; Nisgav, Yael; Weinberger, Dov

2013-06-01

In posterior lamellar keratoplasty procedures such as Descemet stripping endothelial keratoplasty and Descemet membrane endothelial keratoplasty, the lamellar graft is manipulated directly or by injecting an air bubble. This preliminary study sought to evaluate the feasibility of guiding lamellar corneal grafts by generating a magnetic field. Rabbit and porcine Descemet stripping endothelial keratoplasty and Descemet membrane endothelial keratoplasty grafts were manually produced and immersed in a ferromagnetic solution containing nanomagnetic particles conjugated to streptavidin or in gadoteric acid. For the feasibility study, grafts were transferred to an artificial anterior chamber or plastic test tube and a magnetic field was generated with a handheld NdFeB disc magnet. The presence and the sustainability of graft motion were documented under various conditions. For the semiquantitative study, whole or partial grafts were transferred to a plastic test tube after immersion, and the amount of tissue retraction induced by the remote magnet was graded. The grafts were successfully manipulated in all directions by the magnet, from a distance of up to 7 mm. They remained ferromagnetic more than 24 hours after immersion in the ferromagnetic solutions. The degree of retraction was affected by graft size, immersion time, time from immersion, and immersion solution. Posterior lamellar corneal grafts may be made ferromagnetic and remotely manipulated by creation of a magnetic field. The ferromagnetic properties are adjustable. This technique holds promise in attaching and repositioning grafts during keratoplasty. Further research is needed to assess the possible effects of ferromagnetic solutions on corneal endothelial cells and on lamellar graft clarity.

Study of the Influence of adding styrene-ethylene/butadiene-styrene in acrylonitrile-butadiene-styrene and polyethylene blends

OpenAIRE

Peydro, M. A.; Parres, F.; Navarro Vidal, Raúl; Sanchez-Caballero, Samuel

2014-01-01

This work studies the recovery of two grades of acrylonitrile butadiene styrene (ABS) contaminated with low-density polyethylene (LDPE), by adding styrene ethylene/butadiene styrene (SEBS). To simulate contaminated ABS, virgin ABS was mixed with 1, 2, 4, and 8% of LDPE and then extruded at 220°C. After this, the ABS with the highest percentage of LDPE (8%) was mixed with 1, 2, 4, and 8% of SEBS and then extruded. Different blends were mechanically, rheologically, optically, and dimensionally ...

Multiple patterns of diblock copolymer confined in irregular geometries with soft surface

Science.gov (United States)

Li, Ying; Sun, Min-Na; Zhang, Jin-Jun; Pan, Jun-Xing; Guo, Yu-Qi; Wang, Bao-Feng; Wu, Hai-Shun

2015-12-01

The different confinement shapes can induce the formation of various interesting and novel morphologies, which might inspire potential applications of materials. In this paper, we study the directed self-assembly of diblock copolymer confined in irregular geometries with a soft surface by using self-consistent field theory. Two types of confinement geometries are considered, namely, one is the concave pore with one groove and the other is the concave pore with two grooves. We obtain more novel and different structures which could not be produced in other two-dimensional (2D) confinements. Comparing these new structures with those obtained in regular square confinement, we find that the range of ordered lamellae is enlarged and the range of disordered structure is narrowed down under the concave pore confinement. We also compare the different structures obtained under the two types of confinement geometries, the results show that the effect of confinement would increase, which might induce the diblock copolymer to form novel structures. We construct the phase diagram as a function of the fraction of B block and the ratio of h/L of the groove. The simulation reveals that the wetting effect of brushes and the shape of confinement geometries play important roles in determining the morphologies of the system. Our results improve the applications in the directed self-assembly of diblock copolymer for fabricating the irregular structures. Project supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20121404110004), the Research Foundation for Excellent Talents of Shanxi Provincial Department of Human Resources and Social Security, China, and the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi Province, China.

Spontaneous subconjunctival abscess in congenital lamellar ichthyosis

Directory of Open Access Journals (Sweden)

Shivanand C Bubanale

2018-01-01

Full Text Available Congenital lamellar ichthyosis is an autosomal recessive, heterogeneous disorder presenting at birth with generalized skin involvement. The most common ophthalmic manifestation noted is bilateral ectropion of the lower eyelids. A 1-month-old female neonate, the second born of a nonconsanguineous marriage, presented with 4 days' history of redness, discharge, and swelling in the right eye. There was severe right upper eyelid ectropion, conjunctival injection, chemosis, a subconjunctival mass on the temporal bulbar conjunctiva spontaneously draining pus and corneal haze. The anterior chamber, iris, lens and fundus appeared normal. Congenital lamellar ichthyosis was suspected because of scaling and excessive dryness of the entire body. The occurrence of a spontaneous subconjunctival abscess is not known in lamellar ichthyosis. We thus report the management of a rare case of unilateral upper eyelid ectropion, subconjunctival abscess with orbital cellulitis in congenital lamellar ichthyosis.

Order-Order Transition of C → sdG → sL → S in ABC Triblock Copolymer Thin Film Induced by Solvent Vapor.

Science.gov (United States)

Luo, Chunxia; Huang, Weihuan; Han, Yanchun

2009-04-01

The morphology transition of polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock thin film induced in benzene vapor showing weak selectivity for PS is investigated. The order-order transitions (OOT) in the sequence of core-shell cylinders (C), sphere in 'diblock gyroid' (sdG), sphere in lamella (sL) and sphere (S) are observed. The projection along (111) direction in Gyroid phase (sdG(111)) is found to epitaxially grow from C(001) in the film. Instead of sdG(111), sdG(110)(0.1875) develops to the phase of sL. Consequently, the film experiences the transition sequence of sdG(111) → sdG(211) → sdG(110)(0.25)  → sdG(110)(0.1875) between C and sL. The mechanism is analyzed from the total surface area of the blocks. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamics and order-disorder transitions in bidisperse diblock copolymer blends

International Nuclear Information System (INIS)

Wang Yueqiang; Li Xuan; Tang Ping; Yang Yuliang

2011-01-01

We employ the dynamic extension of self-consistent field theory (DSCFT) to study dynamics and order-disorder transitions (ODT) in AB diblock copolymer binary mixtures of two different monodisperse chain lengths by imitating the dynamic storage modulus G' corresponding to any given morphology in the oscillatory shear measurements. The different polydispersity index (PDI) is introduced by binary blending AB diblock copolymers with variations in chain lengths and chain number fractions. The simulation results show that the increase of polydispersity in the minority or symmetric block introduces a decrease in the segregation strength at the ODT, (χN) ODT , whereas the increase of polydispersity in the majority block results in a decrease, then increase and final decrease again in (χN) ODT . To the best of our knowledge, our DSCFT simulations, for the first time, predict an increase in (χN) ODT with the PDI in the majority block, which produces the experimental results. The simulations by previous SCFT, which generally speaking, is capable of describing equilibrium morphologies, however, contradict the experimental data. The polydispersity acquired by properly tuning the chain lengths and number fractions of binary diblock copolymer blends should be a convenient and efficient way to control the microphase separation strength at the ODT. -- Research highlights: → Order-disorder transition in AB diblock copolymer mixtures is investigated using DSCFT. → Microphase separation strength at the ODT increases with PDI in the majority block. → Microphase separation strength at the ODT decreases with PDI in the minority block. → Introduction of polydispersity is efficient to control microphase separation strength at the ODT.

Surface Roughening of Polystyrene and Poly(methyl methacrylate in Ar/O2 Plasma Etching

Directory of Open Access Journals (Sweden)

Amy E. Wendt

2010-12-01

Full Text Available Selectively plasma-etched polystyrene-block-poly(methyl methacrylate (PS-b-PMMA diblock copolymer masks present a promising alternative for subsequent nanoscale patterning of underlying films. Because mask roughness can be detrimental to pattern transfer, this study examines roughness formation, with a focus on the role of cross-linking, during plasma etching of PS and PMMA. Variables include ion bombardment energy, polymer molecular weight and etch gas mixture. Roughness data support a proposed model in which surface roughness is attributed to polymer aggregation associated with cross-linking induced by energetic ion bombardment. In this model, RMS roughness peaks when cross-linking rates are comparable to chain scissioning rates, and drop to negligible levels for either very low or very high rates of cross-linking. Aggregation is minimal for very low rates of cross-linking, while very high rates produce a continuous cross-linked surface layer with low roughness. Molecular weight shows a negligible effect on roughness, while the introduction of H and F atoms suppresses roughness, apparently by terminating dangling bonds. For PS etched in Ar/O2 plasmas, roughness decreases with increasing ion energy are tentatively attributed to the formation of a continuous cross-linked layer, while roughness increases with ion energy for PMMA are attributed to increases in cross-linking from negligible to moderate levels.

Structure, viscoelasticity, and interfacial dynamics of a model polymeric bicontinuous microemulsion

Energy Technology Data Exchange (ETDEWEB)

Hickey, Robert J.; Gillard, Timothy M.; Irwin, Matthew T.; Lodge, Timothy P.; Bates, Frank S. (UMM)

2016-01-01

We have systematically studied the equilibrium structure and dynamics of a polymeric bicontinuous microemulsion (BμE) composed of poly(cyclohexylethylene) (PCHE), poly(ethylene) (PE), and a volumetrically symmetric PCHE–PE diblock copolymer, using dynamic mechanical spectroscopy, small angle X-ray and neutron scattering, and transmission electron microscopy. The BμE was investigated over an 80 °C temperature range, revealing a structural evolution and a rheological response not previously recognized in such systems. As the temperature is reduced below the point associated with the lamellar-disorder transition at compositions adjacent to the microemulsion channel, the interfacial area per chain of the BμE approaches that of the neat (undiluted) lamellar diblock copolymer. With increasing temperature, the diblock-rich interface swells through homopolymer infiltration. Time–temperature-superposed linear dynamic data obtained as a function of frequency show that the viscoelastic response of the BμE is strikingly similar to that of the fluctuating pure diblock copolymer in the disordered state, which we associate with membrane undulations and the breaking and reforming of interfaces. This work provides new insights into the structure and dynamics that characterize thermodynamically stable BμEs in the limits of relatively weak and strong segregation.

Ionizing radiation effect study by electron beam on acrylonitrile butadiene styrene - ABS terpolymer

International Nuclear Information System (INIS)

Landi, Tania Regina Lourenco

2003-01-01

The great advantage in the researches involving development has as objective to increase significantly the quality of the products. The ABS (acrylonitrile, butadiene, styrene) resins are terpolymers formed by an elastomer and two thermoplastics amorphous components. The three different monomeric units from the terpolymer ABS contribute separately to the material characteristics exhibited. The molecular stiffness originating from polystyrene and the benzene ring hanging on the chain is responsible for the flexion module ABS. The acrylonitrile and the styrene incorporated butadiene exercises strong influence in the resistance to the impact because it reduces the bonding among them. The engineering use of this terpolymer became important due their mechanical properties and mainly, for the responses of this to tensions or deformations applied. The polymeric materials, when submitted to the ionizing radiation are modified by the transference of energy to these materials, introducing excitation and ionization of the molecules, generating chemical reactions that can produce permanent modifications in the polymeric physicochemical structure. The induced modifications can result in the polymeric material degradation or crosslinking, which can result in the improvement of some properties. This work has, as objective, to study the electron beam ionizing radiation effect, at different doses, in the properties of the polymer ABS. The studied properties were: tensile strength at break, elongation at break, Izod impact strength, flexural strength, melt flow index, Vicat softening temperature and the thermic distortion temperature. Also researches on Differential Scanning Calorimetry (DSC) and Thermogravimetric Analyses (TGA) were accomplished. From the experimental results, it was showed that for doses until 500 kGy, at 22.6 kGy/s dose rate, in the presence of air, the crosslinking process of ABS prevails. (author)

Diblock Terpolymers Are Tunable and pH Responsive Vehicles To Increase Hydrophobic Drug Solubility for Oral Administration.

Science.gov (United States)

Tale, Swapnil; Purchel, Anatolii A; Dalsin, Molly C; Reineke, Theresa M

2017-11-06

Synthetic polymers offer tunable platforms to create new oral drug delivery vehicles (excipients) to increase solubility, supersaturation maintenance, and bioavailability of poorly aqueous soluble pharmaceutical candidates. Five well-defined diblock terpolymers were synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT) and consist of a first block of either poly(ethylene-alt-propylene) (PEP), poly(N-isopropylacrylamide) (PNIPAm), or poly(N,N-diethylaminoethyl methacrylate) (PDEAEMA) and a second hydrophilic block consisting of a gradient copolymer of N,N-dimethylacrylamide (DMA) and 2-methacrylamidotrehalose (MAT). This family of diblock terpolymers offers hydrophobic, hydrophilic, or H-bonding functionalities to serve as noncovalent sites of drug binding. Drug-polymer spray dried dispersions (SDDs) were created with a model drug, probucol, and characterized by differential scanning calorimetry (DSC). These studies revealed that probucol crystallinity decreased with increasing H-bonding sites available in the polymer. The PNIPAm-b-P(DMA-grad-MAT) systems revealed the best performance at pH 6.5, where immediate probucol release and effective maintenance of 100% supersaturation was found, which is important for facilitating drug solubility in more neutral conditions (intestinal environment). However, the PDEAEMA-b-P(DMA-grad-MAT) system revealed poor probucol dissolution at pH 6.5 and 5.1. Alternatively, at an acidic pH of 3.1, a rapid and high dissolution profile and effective supersaturation maintenance of up to 90% of the drug was found, which could be useful for triggering drug release in acidic environments (stomach). The PEP-b-P(DMA-grad-MAT) system showed poor performance (only ∼20% of drug solubility at pH 6.5), which was attributed to the low solubility of the polymers in the dissolution media. This work demonstrates the utility of diblock terpolymers as a potential new excipient platform to optimize design parameters for

Preparations, Properties, and Applications of Periodic Nano Arrays using Anodized Aluminum Oxide and Di-block Copolymer

Science.gov (United States)

Noh, Kunbae

2011-12-01

Self-ordered arrangements observed in various materials systems such as anodic aluminum oxide, polystyrene nanoparticles, and block copolymer are of great interest in terms of providing new opportunities in nanofabrication field where lithographic techniques are broadly used in general. Investigations on self-assembled nano arrays to understand how to obtain periodic nano arrays in an efficient yet inexpensive way, and how to realize advanced material and device systems thereof, can lead to significant impacts on science and technology for many forefront device applications. In this thesis, various aspects of periodic nano-arrays have been discussed including novel preparations, properties and applications of anodized aluminum oxide (AAO) and PS-b-P4VP (S4VP) di-block copolymer self-assembly. First, long-range ordered AAO arrays have been demonstrated. Nanoimprint lithography (NIL) process allowed a faithful pattern transfer of the imprint mold pattern onto Al thin film, and interesting self-healing and pattern tripling phenomena were observed, which could be applicable towards fabrication of the NIL master mold having highly dense pattern over large area, useful for fabrication of a large-area substrate for predictable positioning of arrayed devices. Second, S4VP diblock copolymer self-assembly and S4VP directed AAO self-assembly have been demonstrated in the Al thin film on Si substrate. Such a novel combination of two dissimilar self-assembly techniques demonstrated a potential as a versatile tool for nanopatterning formation on a Si substrate, capable of being integrated into Si process technology. As exemplary applications, vertically aligned Ni nanowires have been synthesized into an S4VP-guided AAO membrane on a Si substrate in addition to anti-dot structured [Co/Pd]n magnetic multilayer using S4VP self assembly. Third, a highly hexagonally ordered, vertically parallel aluminum oxide nanotube array was successfully fabricated via hard anodization technique

On the crystallization behavior of syndiotactic-b-atactic polystyrene stereodiblock copolymers, atactic/syndiotactic polystyrene blends, and aPS/sPS blends modified with sPS-b-aPS

Energy Technology Data Exchange (ETDEWEB)

Annunziata, Liana, E-mail: liana.annunziatta@univ-rennes1.fr [Organométalliques et Catalyse, UMR 6226 Sciences Chimiques CNRS, Université de Rennes 1, Campus de Beaulieu, F-35042 Rennes Cedex (France); Monasse, Bernard, E-mail: bernard.monasse@mines-paristech.fr [Mines-ParisTech, CEMEF, Centre de Mise en Forme des Matériaux, UMR CNRS 7635, Sophia Antipolis (France); Rizzo, Paola; Guerra, Gaetano [Dipartimento di Chimica e Biologia, Università degli studi di Salerno, Via Ponte don Melillo, I-84084 Fisciano, SA (Italy); Duc, Michel [Total Petrochemicals Research Feluy, Zone Industrielle Feluy C, B-7181 Seneffe (Belgium); Carpentier, Jean-François, E-mail: jean-francois.carpentier@univ-rennes1.fr [Organométalliques et Catalyse, UMR 6226 Sciences Chimiques CNRS, Université de Rennes 1, Campus de Beaulieu, F-35042 Rennes Cedex (France)

2013-09-16

Crystallization and morphological features of syndiotactic-b-atactic polystyrene stereodiblock copolymers (sPS-b-aPS), atactic/syndiotactic polystyrene blends (aPS/sPS), and aPS/sPS blends modified with sPS-b-aPS, with different compositions in aPS and sPS, have been investigated using differential scanning calorimetry (DSC), polarized light optical microscopy (POM) and wide angle X-ray diffraction (WAXRD) techniques. For comparative purposes, the properties of parent pristine sPS samples were also studied. WAXRD analyses revealed for all the samples, independently from their composition (aPS/sPS ratio) and structure (blends, block copolymers, blends modified with block copolymers), the same polymorphic β form of sPS. The molecular weight of aPS and sPS showed opposite effects on the crystallization of 50:50 aPS/sPS blends: the lower the molecular weight of aPS, the slower the crystallization while the lower the molecular weight of sPS, the faster the crystallization. DSC studies performed under both isothermal and non-isothermal conditions, independently confirmed by POM studies, led to a clear trend for the crystallization rate at a given sPS/aPS ratio (ca. 50:50 and 20:80): sPS homopolymers > sPS-b-aPS block copolymers ∼sPS/aPS blends modified with sPS-b-aPS copolymers > sPS/aPS blends. Interestingly, sPS-b-aPS block copolymers not only crystallized faster than blends, but also affected positively the crystallization behavior of blends. At 50:50 sPS/aPS ratio, blends (Blend-2), block copolymers (Cop-1) and blends modified with block copolymers (Blend-2-mod) crystallized via spherulitic crystalline growth controlled by an interfacial process. In all cases, an instantaneous nucleation was observed. The density of nuclei in block copolymers (160,000−190,000 nuclei mm{sup −3}) was always higher than that in blends and modified blends (30,000−60,000 nuclei mm{sup −3}), even for quite different sPS/aPS ratio. At 20:80 sPS/aPS ratio, the block copolymers

Study of lamellar structure and crystallization behavior of poly(butylene terephthalate (PBT) in PBT/ABS and PBT/ABS/MMA-GMA blends using DSC, SAXS and DMTA

International Nuclear Information System (INIS)

Mantovani, Gerson L.; Pessan, Luiz A.; Hage, Elias; Torriani, Iris L.

2001-01-01

The effects of processing conditions and blend composition in the crystallization behaviour and lamellar structure of poly(butylene terephthalate) (PBT) in blends with acrylonitrile-butadiene-styrene copolymer (ABS) were studied. Differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and dynamic mechanical thermal analysis (DMTA) were used to observe those effects. Addition of reactive acrylic compatibilizer to the PBT/ABS blends has promoted an increase in the heat of crystallization of the related blends. The Long Period (L), obtained from the peak in the Lorentz-corrected SAXS pattern, was used to observe the effect in the lamellar structure of PBT phase in the blends. The results were in good agreement with the calculated values from de correlation function and the values of L do not show a significant dependence with the PBT mass fraction, either in the binary blends (PBT/ABS) or in the compatibilized blends. A slight but clear increase of the long period (from 3 to 5 angstrom) is noted for the systems injection molded at 240 deg C when compared to the ones molded at 260 deg C, although PBT crystallinity in the blends does not change significantly with blend composition or processing conditions. DMTA curves show a slight shift in the temperature of the tan δ main peaks for both PBT and ABS phases in the compatibilized blends, thereby indicating changes in the degree of miscibility or interaction between phases of those blends. Changes in the compatibilized blends miscibility may be responsible by the effects in the crystallization behaviour and lamellar structure of the PBT/ABS blends. (author)

Study of lamellar structure and crystallization behavior of poly(butylene terephthalate (PBT) in PBT/ABS and PBT/ABS/MMA-GMA blends using DSC, SAXS and DMTA

Energy Technology Data Exchange (ETDEWEB)

Mantovani, Gerson L.; Pessan, Luiz A.; Hage, Elias [Sao Carlos Univ., SP (Brazil). Dept. de Engenharia de Materiais]. E-mail: elias@power.ufscar.br; Plivelic, Tomas S. [Laboratorio Nacional de Luz Sincrotron (LNLS), Campinas, SP (Brazil); Torriani, Iris L. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Fisica Gleb Wataghin

2001-07-01

The effects of processing conditions and blend composition in the crystallization behaviour and lamellar structure of poly(butylene terephthalate) (PBT) in blends with acrylonitrile-butadiene-styrene copolymer (ABS) were studied. Differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and dynamic mechanical thermal analysis (DMTA) were used to observe those effects. Addition of reactive acrylic compatibilizer to the PBT/ABS blends has promoted an increase in the heat of crystallization of the related blends. The Long Period (L), obtained from the peak in the Lorentz-corrected SAXS pattern, was used to observe the effect in the lamellar structure of PBT phase in the blends. The results were in good agreement with the calculated values from de correlation function and the values of L do not show a significant dependence with the PBT mass fraction, either in the binary blends (PBT/ABS) or in the compatibilized blends. A slight but clear increase of the long period (from 3 to 5 angstrom) is noted for the systems injection molded at 240 deg C when compared to the ones molded at 260 deg C, although PBT crystallinity in the blends does not change significantly with blend composition or processing conditions. DMTA curves show a slight shift in the temperature of the tan {delta} main peaks for both PBT and ABS phases in the compatibilized blends, thereby indicating changes in the degree of miscibility or interaction between phases of those blends. Changes in the compatibilized blends miscibility may be responsible by the effects in the crystallization behaviour and lamellar structure of the PBT/ABS blends. (author)

Thermal processing of diblock copolymer melts mimics metallurgy

Science.gov (United States)

Kim, Kyungtae; Schulze, Morgan W.; Arora, Akash; Lewis, Ronald M.; Hillmyer, Marc A.; Dorfman, Kevin D.; Bates, Frank S.

2017-05-01

Small-angle x-ray scattering experiments conducted with compositionally asymmetric low molar mass poly(isoprene)-b-poly(lactide) diblock copolymers reveal an extraordinary thermal history dependence. The development of distinct periodic crystalline or aperiodic quasicrystalline states depends on how specimens are cooled from the disordered state to temperatures below the order-disorder transition temperature. Whereas direct cooling leads to the formation of documented morphologies, rapidly quenched samples that are then heated from low temperature form the hexagonal C14 and cubic C15 Laves phases commonly found in metal alloys. Self-consistent mean-field theory calculations show that these, and other associated Frank-Kasper phases, have nearly degenerate free energies, suggesting that processing history drives the material into long-lived metastable states defined by self-assembled particles with discrete populations of volumes and polyhedral shapes.

Serotyping of Actinobacillus pleuropneumoniae serotype 5 strains using a monoclonal-based polystyrene agglutination test

DEFF Research Database (Denmark)

Dubreuil, J.D.; Letellier, A.; Stenbæk, Eva

1996-01-01

A polystyrene agglutination test has been developed for serotyping Actinobacillus pleuropneumoniae serotype 5a and 5b strains. Protein A-coated polystyrene microparticles were sensitized with a murine monoclonal antibody recognizing an epitope on serotype 5 LPS-O chain as shown by SDS-PAGE and We......A polystyrene agglutination test has been developed for serotyping Actinobacillus pleuropneumoniae serotype 5a and 5b strains. Protein A-coated polystyrene microparticles were sensitized with a murine monoclonal antibody recognizing an epitope on serotype 5 LPS-O chain as shown by SDS...... suspension of bacterial cells grown for 18 h. All A, pleuropneumoniae strains had been previously serotyped using standard procedures, The polystyrene agglutination test was rapid (less than 3 min) and easy to perform. Overall a very good correlation (97.3%) with the standard techniques was found...

Preparation of textural lamellar tin deposits via electrodeposition

Science.gov (United States)

Wen, Xiaoyu; Pan, Xiaona; Wu, Libin; Li, Ruinan; Wang, Dan; Zhang, Jinqiu; Yang, Peixia

2017-06-01

Lamellar tin deposits were prepared by galvanostatical electroplating from the aqueous acidic-sulfate bath, with gelatin and benzalacetone dissolved in ethanol (ABA+EtOH) as additive, and their morphologies were investigated by scanning electron microscopy. Cathodic polarization curves revealed that the absorbability of ABA+EtOH on the cathode surface was higher than that of gelatin. X-ray diffraction analysis indicated preferred orientations of tin growth led to the formation of lamellar structure and distortion of tin lattice. The growth mechanism of lamellar tin was also discussed.

Oligosaccharides and glycolipids addition in charged lamellar phases

International Nuclear Information System (INIS)

Ricoul, F.

1997-01-01

The aim of this work is to study the addition of oligosaccharides and glycolipids in lamellar phases of the cationic surfactant DDAB (di-dodecyl-dimethyl-ammonium bromide). Two steps have been followed: the determination of phases prisms and the thermodynamic interpretation in terms of molecular interactions. In order to characterize these systems, two new experimental small angle scattering methods have been perfected: 1) a neutron scattering contrast variation method which allows to study the adsorption of aqueous solution in bilayers and 2) a capillary concentration gradient method to establish directly and quantitatively the phases diagrams of ternary systems by X rays scattering. It has been pointed out that the oligosaccharides induce a depletion attractive force on the lamellar-lamellar equilibrium of the DDAB when they are excluded of the most concentrated phase. For the two studied glycolipids: 2-O lauroyl-saccharose and N-lauroyl N-nonyl lactitol, the ternary phase diagrams water-DDAB-glycolipid have been established in terms of temperature. Critical points at ambient temperature have been given. The osmotic pressure in concentrated lamellar phases has been measured. It has been shown that glycolipids increase the hydration repulsion at short distance and that the electrostatic repulsion is outstanding and unchanged at high distance if there is at less 1 mole percent of ionic surfactant. In a dilute solution, glycolipids decrease the maximum swelling of lamellar phases, with a competition between the lamellar phase and the micellae dilute phase for water. (O.M.)

Congenital lamellar ichthyosis, a case report.

OpenAIRE

Joaquín Saavedra D.; María José Sierralta S.; Cristian Saavedra D; Vanesa Rivera C; Francisco Cerda C.

2014-01-01

ABSTRACT INTRODUCTION: Lamellar Ichthyosis is a rare skin diseases belonging to the Group of the so-called genodermatoses. It is a form of congenital ichthyosis evident at birth. CASE REPORT: Male neonate, born at 36 weeks of gestation via cesarian section, appropriate for gestational age and Apgar Score 8. Nonconsanguineous parents. Affected brother with Ichthyosis lamellar. Is hospitalized in the Neonatal Intermediary Care Unit of the Hospital of San Fernando due to ...

Dye-sensitized PS-b-P2VP-templated nickel oxide films for photoelectrochemical applications.

Science.gov (United States)

Massin, Julien; Bräutigam, Maximilian; Kaeffer, Nicolas; Queyriaux, Nicolas; Field, Martin J; Schacher, Felix H; Popp, Jürgen; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin; Artero, Vincent

2015-06-06

Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push-pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices.

Self-oscillating AB diblock copolymer developed by post modification strategy

Energy Technology Data Exchange (ETDEWEB)

Ueki, Takeshi, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp; Onoda, Michika; Tamate, Ryota; Yoshida, Ryo, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Shibayama, Mitsuhiro [Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwano-ha, Kashiwa, Chiba 277-8581 (Japan)

2015-06-15

We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy){sub 3}), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy){sub 3} was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy){sub 3} vinyl monomer and (ii) post modification (PM) of Ru(bpy){sub 3} with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔT{sub m}), where the block copolymer self-assembles into micelle at reduced Ru(bpy){sub 3}{sup 2+} state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy){sub 3}{sup 3+} state, monotonically extends as the composition of the Ru(bpy){sub 3} increases. The ΔT{sub m} of the block copolymer prepared by PM is larger than that by DP. The difference in ΔT{sub m} is rationalized from the statistical analysis of the arrangement of the Ru(bpy){sub 3} moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔT{sub m} (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.

Transformations to and from the gyroid phase in a diblock copolymer

DEFF Research Database (Denmark)

Vigild, Martin Etchells; Almdal, Kristoffer; Mortensen, K

1998-01-01

the ordered phases and the order-order transitions exhibited by a poly(ethylene-alt-propylene)-poly-(dimethylsiloxane) diblock copolymer. An intermediate structure-very similar to the hexagonal perforated layer (HPL) phase reported in other diblock systems-proves to be metastable, and we study the kinetics...... and epitaxy of its relaxation to the "gyroid" phase of Ia (3) over bar d symmetry. Likewise we study the relaxation of a supercooled hexagonal phase to the gyroid structure and also observe that the gyroid phase is bypassed in a slow cool from the hexagonal phase to the HPL-like structure. The origin...

Preparation of butadiene D{sub 6} -1-1-2-3-4-4; Preparation du butadiene D{sub 6} -1-1-2-3-4-4

Energy Technology Data Exchange (ETDEWEB)

Pichat, L; Chatelain, G [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

1959-07-01

A description of the preparation of butadiene D{sub 6} by dehalogenation of perchlorobutadiene by zinc and heavy water in dioxane. (author) [French] Description de la preparation du butadiene D{sub 6} par reduction deshalogenante du perchlorobutadiene par le zinc et l'eau lourde dans le dioxane. (auteur)

46 CFR 154.1750 - Butadiene or vinyl chloride: Refrigeration system.

Science.gov (United States)

2010-10-01

... and Operating Requirements § 154.1750 Butadiene or vinyl chloride: Refrigeration system. A... 46 Shipping 5 2010-10-01 2010-10-01 false Butadiene or vinyl chloride: Refrigeration system. 154.1750 Section 154.1750 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK...

[Indications and surgical approach for lamellar macular holes and pseudoholes].

Science.gov (United States)

Haritoglou, C; Schumann, R G

2017-12-01

This article presents a discussion on the indications for surgical interventions of lamellar macular holes and pseudoholes. What are the criteria for deciding on the surgical intervention for lamellar macular holes and pseudoholes? The article is based on a literature search in PubMed RESULTS: Lamellar macular holes and pseudoholes are subdivided into degenerative and tractive alterations. Both entities are associated with relatively specific morphological and functional criteria, which correlate with the expected functional and morphological results of the surgical intervention. Patients with pseudoholes therefore profit more from a surgical intervention because alterations to the outer retina are less pronounced in these cases. The indications for surgery of lamellar macular holes and pseudoholes are established by the type of lamellar defect and the morphological and functional alterations associated with this condition.

Numerical investigation of the contraction of neutral-charged diblock copolymer brushes in electric fields

International Nuclear Information System (INIS)

Chen, Yuwei; Li, Haiming; Zhu, Yuejin; Tong, Chaohui

2016-01-01

Using self-consistent field theory (SCFT), the contraction of neutral-charged A-B diblock copolymer brushes in electric fields generated by opposite surface charges on two parallel electrodes has been numerically investigated. The diblock copolymer chains were grafted with the free end of the neutral block to one electrode and immersed in a salt-free solution sandwiched between the two electrodes. The numerical results reveal that the charged monomers, A-B joint segment and the tail exhibit bimodal distributions under external electric fields, which are absent for homopolymer polyelectrolyte brushes. The dependences of the relative populations and peak positions of the two modes on various parameters such as block ratio, grafting density, chain length and strength of the applied electric field were systematically examined and the underlining mechanisms were elucidated. It was found in this study that, if the total amount of surface charges on the grafting electrode is no more than that of the counter-ions in the system, overall charge neutrality is generally maintained inside the brushes when including the contribution of surface charges on the grafting electrode. In such a case, the counter-ions expelled from the brushes are highly enriched in the immediate vicinity of the second electrode and an approximate charge balance between these expelled counter-ions and the opposite surface charges on the second electrode is achieved. (paper)

Tough, semiconducting polyethylene-poly(3-hexylthiophene) diblock copolymers

DEFF Research Database (Denmark)

Müller, C.; Goffri, S.; Breiby, Dag Werner

2007-01-01

Semiconducting diblock copolymers of polyethylene (PE) and regioregular poly(3-hexylthiophene) (P3HT) are demonstrated to exhibit a rich phase behaviour, judicious use of which permitted us to fabricate field-effect transistors that show saturated charge carrier mobilities, mu(FET), as high as 2 x...

Species difference in metabolism of inhaled butadiene

International Nuclear Information System (INIS)

Sabourin, P.J.; Dahl, A.R.; Bechtold, W.E.; Henderson, R.F.; Burka, L.T.

1991-01-01

Chronic exposure of B6C3F 1 mice and Sprague-Dawley rats to butadiene (BD) produced a very high incidence of cancer in mice while the incidence in rats was much lower with different tissues affected. Studies at this institute indicate that for equivalent exposures, the blood BD epoxide concentrations in mice are 5-fold higher than in rats and > 10-fold higher than in Cynomolgus monkeys. In this study, the profiles of urinary metabolites of butadiene were determined in Cynomolgus monkeys, F344/N rats, Sprague Dawley rats, B6C3F 1 mice and Syrian hamsters, species containing widely divergent hepatic epoxide hydrolase (EH) activities. Animals were exposed for 2 hr to 8,000 ppm [ 14 C]BD and 24-hr urine samples were analyzed for metabolites. Two major urinary metabolites were identified, N-acetyl-S-(-1(or 2)-3-butene-2(or 1)-ol)cysteine (1) and N-acetyl-S-(-4-butane-1,2-diol)cysteine (2). Monkeys exposed by inhalation produced primarily metabolite 2, while rodent species produced 1-4 times as much of 1 compared to 2. The ratio of 2/1 formation was related to the hepatic epoxide hydrolase activity in different species. The high 2/1 ratio in monkeys was consistent with the lower blood epoxide levels in this species. If BD metabolism by humans is similar to that in the monkey, exposure of humans to BD may result in lower tissue concentrations of reactive metabolites than an equivalent exposure of rodents. This has important implications for assessing the risk to humans of BD exposure based on rodent studies

Polybenzoxazole-filled nitrile butadiene rubber compositions

Science.gov (United States)

Gajiwala, Himansu M. (Inventor); Guillot, David G. (Inventor)

2008-01-01

An insulation composition that comprises at least one nitrile butadiene rubber (NBR) having an acrylonitrile content that ranges from approximately 26% by weight to approximately 35% by weight and polybenzoxazole (PBO) fibers. The NBR may be a copolymer of acrylonitrile and butadiene and may be present in the insulation composition in a range of from approximately 45% by weight to approximately 56% by weight of a total weight of the insulation composition. The PBO fibers may be present in a range of from approximately 3% by weight to approximately 10% by weight of a total weight of the insulation composition. A rocket motor including the insulation composition and a method of insulating a rocket motor are also disclosed.

Distributions of chain ends and junction points in ordered block copolymers

International Nuclear Information System (INIS)

Mayes, A.M.; Johnson, R.D.; Russell, T.P.; Smith, S.D.; Satija, S.K.; Majkrzak, C.F.

1993-01-01

Chain configurations in ordered symmetric poly(styrene-b-methyl methacrylate) diblock copolymers were examined by neutron reflectively. In a thin-film geometry the copolymers organize into lamellar microdomains oriented parallel to the substrate surface. The copolymers organize into lamellar microdomains oriented parallel to the substrate surface. The copolymers were synthesized with small fractions of deuterated segments at either the chain ends or centers. This selective labeling permitted characterization of the spatial distribution of chain ends and junction points normal to the plane of the film. From the reflectivity analysis, the junction points are found to be confined to the PS/PMMA interfacial regions. The chain ends, however, are well distributed through their respective domains, exhibiting only a weak maximum in concentration at the center of the domains

Cylindrical-confinement-induced phase behaviours of diblock copolymer melts

International Nuclear Information System (INIS)

Mei-Jiao, Liu; Shi-Ben, Li; Lin-Xi, Zhang; Xiang-Hong, Wang

2010-01-01

The phase behaviours of diblock copolymers under cylindrical confinement are studied in two-dimensional space by using the self-consistent field theory. Several phase parameters are adjusted to investigate the cylindrical-confinement-induced phase behaviours of diblock copolymers. A series of lamella-cylinder mixture phases, such as the mixture of broken-lamellae and cylinders and the mixture of square-lamellae and cylinders, are observed by varying the phase parameters, in which the behaviours of these mixture phases are discussed in the corresponding phase diagrams. Furthermore, the free energies of these mixture phases are investigated to illustrate their evolution processes. Our results are compared with the available observations from the experiments and simulations respectively, and they are in good agreement and provide an insight into the phase behaviours under cylindrical confinement. (cross-disciplinary physics and related areas of science and technology)

B10(n,α)Li7 irradiation effects on high impact polystyrene

International Nuclear Information System (INIS)

Gupta, M.C.; Bansod, V.P.

1984-01-01

Irradiation effects of B 10 (n,α)Li 7 charged particles on high impact polystyrene were compared with those of Co 60 γ-rays, from the viewpoint of linear energy transfer (LET). For irradiation in air, the G values of crosslinks and main-chain scissions, G(X) and G(S) are 0.018 and 0.06, respectively, for γ-rays of low LET (ca. 0.22 eV/nm). Charged particles [B 10 (n,α)Li 7 ] of high LET (ca. 280 eV/nm) increase the G(X) value to 0.15 but G(S) is not much affected. All these findings are explained qualitatively by a difference in the distribution of energy deposition and the mechanism involving the competition between the deactivation of an excited molecule by the collision with ground state molecules and the macroradical formation by the bimolecular reaction of the excited molecules. These excited molecules in HIPS might be produced more closely to one another by charged particles than by γ-rays. (author)

Mode-coupling theory of self-diffusion in diblock copolymers. II. Model calculations and experimental comparisons

International Nuclear Information System (INIS)

Guenza, M.; Schweizer, K.S.

1998-01-01

The predictions of polymer-mode-coupling theory for self-diffusion in entangled structurally and interaction symmetric diblock copolymer fluids are illustrated by explicit numerical calculations. We find that retardation of translational motion emerges near and somewhat below the order endash disorder transition (ODT) in an approximately exponential and/or thermally activated manner. At fixed reduced temperature, suppression of diffusion is enhanced with increasing diblock molecular weight, compositional symmetry, and/or copolymer concentration. At very low temperatures, a new entropic-like regime of mobility suppression is predicted based on an isotropic supercooled liquid description of the copolymer structure. Preliminary generalization of the theory to treat diblock tracer diffusion is also presented. Quantitative applications to recent self and tracer diffusion measurements on compositionally symmetric polyolefin diblock materials have been carried out, and very good agreement between theory and experiment is found. Asymmetry in block local friction constants is predicted to significantly influence mobility suppression, with the largest effects occurring when the minority block is also the high friction species. New experiments to further test the predictions of the theory are suggested. copyright 1998 American Institute of Physics

Thermo-reversible supramolecular hydrogels of trehalose-type diblock methylcellulose analogues.

Science.gov (United States)

Yamagami, Mao; Kamitakahara, Hiroshi; Yoshinaga, Arata; Takano, Toshiyuki

2018-03-01

This paper describes the design and synthesis of new trehalose-type diblock methylcellulose analogues with nonionic, cationic, and anionic cellobiosyl segments, namely 1-(tri-O-methyl-cellulosyl)-4-[β-d-glucopyranosyl-(1→4)-β-d-glucopyranosyloxymethyl]-1H-1,2,3-triazole (1), 1-(tri-O-methyl-cellulosyl)-4-[(6-amino-6-deoxy-β-d-glucopyranosyl)-(1→4)- 6-amino-6-deoxy-β-d-glucopyranosyloxymethyl]-1H-1,2,3-triazole (2), and 4-(tri-O-methyl-cellulosyloxymethyl)-1-[β-d-glucopyranuronosyl-(1→4)-β-d-glucopyranuronosyl]-1H-1,2,3-triazole (3), respectively. Aqueous solutions of all of the 1,2,3-triazole-linked diblock methylcellulose analogues possessed higher surface activities than that of industrially produced methylcellulose and exhibited lower critical solution temperatures, that allowed the formation of thermoresponsive supramolecular hydrogels at close to human body temperature. Supramolecular structures of thermo-reversible hydrogels based on compounds 1, 2, and 3 were investigated by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Detailed structure-property-function relationships of compounds 1, 2, and 3 were discussed. Not only nonionic hydrophilic segment but also ionic hydrophilic segments of diblock methylcellulose analogues were valid for the formation of thermo-reversible supramolecular hydrogels based on end-functionalized methylcellulose. Copyright © 2017 Elsevier Ltd. All rights reserved.

'Smart' Diblock Copolymers as Templates for Magnetic-Core Gold-Shell Nanoparticle Synthesis

International Nuclear Information System (INIS)

Nash, Michael A.; Lai, James J.; Hoffman, Allan S.; Yager, Paul; Stayton, Partick S.

2010-01-01

We report a new strategy for synthesizing temperature-responsive γ-Fe 2 O 3 -core/Au-shell nanoparticles (Au-mNPs) from diblock copolymer micelles. The amphiphilic diblock copolymer chains were synthesized using reversible addition-fragmentation chain-transfer (RAFT) with a thermally responsive 'smart' poly(N-isopropylacrylamide) (pNIPAAm) block and an amine-containing poly(N,N-dimethylaminoethylacrylamide) (DMAEAm) block that acted as a reducing agent during gold shell formation. The Au-mNPs reversibly aggregated upon heating the solution above the transition temperature of pNIPAAm, resulting in a red-shifted localized surface plasmon resonance.

Dynamics of interacting edge defects in copolymer lamellae

Science.gov (United States)

Dalnoki-Veress, Kari; McGraw, Joshua D.; Rowe, Ian D. W.

2011-03-01

It is known that terraces at the interface of lamella forming diblock copolymers do not make discontinuous jumps in height. Rather, their profiles are smoothly varying. The width of the transition region between two lamellar heights is typically several hundreds of nanometres, resulting from a balance between surface tension, chain stretching penalties, and the enthalpy of mixing. What is less well known in these systems is what happens when two transition regions approach one another. In this study, we show that time dependent experimental data of interacting copolymer lamellar edges is consistent with a model that assumes a repulsion between adjacent edges. The range of the interaction between edge defects is consistent with the profile width of noninteracting diblock terraces. Financial support from NSERC of Canada is gratefully acknowledged.

Effects of electric fields on the photonic crystal formation from block copolymers

Science.gov (United States)

Lee, Taekun; Ju, Jin-wook; Ryoo, Won

2012-03-01

Effects of electric fields on the self-assembly of block copolymers have been investigated for thin films of polystyrene-bpoly( 2-vinyl pyridine); PS-b-P2VP, 52 kg/mol-b-57 kg/mol and 133 kg/mol-b-132 kg/mol. Block copolymers of polystyrene and poly(2-vinyl pyridine) have been demonstrated to form photonic crystals of 1D lamellar structure with optical band gaps that correspond to UV-to-visible light. The formation of lamellar structure toward minimum freeenergy state needs increasing polymer chain mobility, and the self-assembly process is accelerated usually by annealing, that is exposing the thin film to solvent vapor such as chloroform and dichloromethane. In this study, thin films of block copolymers were spin-coated on substrates and placed between electrode arrays of various patterns including pin-points, crossing and parallel lines. As direct or alternating currents were applied to electrode arrays during annealing process, the final structure of thin films was altered from the typical 1D lamellae in the absence of electric fields. The formation of lamellar structure was spatially controlled depending on the shape of electrode arrays, and the photonic band gap also could be modulated by electric field strength. The spatial formation of lamellar structure was examined with simulated distribution of electrical potentials by finite difference method (FDM). P2VP layers in self-assembled film were quaternized with methyl iodide vapor, and the remaining lamellar structure was investigated by field emission scanning electron microscope (FESEM). The result of this work is expected to provide ways of fabricating functional structures for display devices utilizing photonic crystal array.

Adsorption of charged diblock copolymers : effect on colloidal stability

NARCIS (Netherlands)

Israels, R.

1994-01-01

In this thesis we present Scheutjens-Fleer (SF) calculations on the adsorption of diblock copolymers. More specifically, we restrict ourselves to adsorption at uncharged surfaces, while the specific type of block copolymers we consider have one uncharged adsorbing "anchor" block and one

Hydroxyl radical and ozone initiated photochemical reactions of 1,3-butadiene

Science.gov (United States)

Liu, Xiaoyu; Jeffries, Harvey E.; Sexton, Kenneth G.

1,3-Butadiene, classified as hazardous in the 1990 Clean Air Act Amendments, is an important ambient air pollutant. Understanding its atmospheric transformation is useful for its own sake, and is also helpful for eliciting isoprene's fate in the atmosphere (isoprene dominates the biogenic emissions in US). In this paper, samples from both hydroxyl- and ozone-initiated photooxidation of 1,3-butadiene were analyzed by derivatization with O- (2,3,4,5,6-pentafluorobenzyl)-hydroxylamine followed by separation and detection by gas chromatography/ion trap mass spectrometry to detect and identify carbonyl compounds. The following carbonyls were observed: formaldehyde, acrolein, glycolaldehyde, glycidaldehyde, 3-hydroxy-propanaldehyde, hydroxy acetone, and malonaldehyde, which can be classified into three categories: epoxy carbonyls, hydroxyl carbonyls, and di-carbonyls. Three non-carbonyls, furan, 1,3-buatdiene monoxide, and 1,3-butadiene diepoxide, were also found. To confirm their identities, both commercially available and synthesized standards were used. To investigate the mechanism of 1,3-butadiene, separate batch reactor experiments for acrolein and 1,3-butadiene monoxide were carried out. Time series samples for several products were also taken. When necessary, computational chemistry methods were also employed. Based on these results, various schemes for the reaction mechanism are proposed.

Research Update: Triblock copolymers as templates to synthesize inorganic nanoporous materials

Directory of Open Access Journals (Sweden)

Yunqi Li

2016-04-01

Full Text Available This review focuses on the application of triblock copolymers as designed templates to synthesize nanoporous materials with various compositions. Asymmetric triblock copolymers have several advantages compared with symmetric triblock copolymers and diblock copolymers, because the presence of three distinct domains can provide more functional features to direct the resultant nanoporous materials. Here we clearly describe significant contributions of asymmetric triblock copolymers, especially polystyrene-block-poly(2-vinylpyridine-block-poly(ethylene oxide (abbreviated as PS-b-P2VP-b-PEO.

Self-Assembly of Charged Amphiphilic Diblock Copolymers with Insoluble Blocks of Decreasing Hydrophobicity: From Kinetically Frozen Colloids to Macrosurfactants

Energy Technology Data Exchange (ETDEWEB)

M Jacquin; P Muller; H Cottet; O Theodoly

2011-12-31

We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 C and 1 M.

Synthesis and characterization of a lamellar hydroxyapatite/DNA nanohybrid

Energy Technology Data Exchange (ETDEWEB)

Zuo Guifu; Wan Yizao; Meng Xianguang [School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Zhao Qing [School of Agriculture and Bioengineering, Tianjin University, Tianjin 300072 (China); Ren Kaijing [Department of Joint Surgery, Tianjin Hospital, Tianjin 300211 (China); Jia Shiru [Key Laboratory of Industrial Microbiology, Ministry of Education, Tianjin University of Science and Technology, 29, 13th Street, TEDA, Tianjin 300457 (China); Wang Jiehua, E-mail: gfzuo@tju.edu.cn [School of Agriculture and Bioengineering, Tianjin University, Tianjin 300072 (China)

2011-04-15

Research highlights: {yields} A lamellar hydroxyapatite (HAp)/DNA nanohybrid was prepared as a novel gene delivering vector. {yields} Gel electrophoresis analysis confirmed that the lamellar HAp could protect DNA from degradation of DNase I. {yields} The protected DNA in the HAp/DNA nanohybrid could be recovered readily under acid conditions. - Abstract: Two-dimensional layered materials exhibit desired functionalities when being used as gene delivery materials. In this study, a novel gene delivering vector, lamellar hydroxyapatite (HAp)/DNA nanohybrid was prepared. The structure of HAp/DNA nanohybrid was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared (FT-IR) spectroscopy analysis revealed that ion-exchange occurred during the process. Gel electrophoresis analysis confirmed that the lamellar HAp could protect DNA from degradation of DNase I and the protected DNA could be recovered readily under acid conditions. Furthermore, the integrity of released DNA was confirmed by UV-vis spectra.

Synthesis and characterization of a lamellar hydroxyapatite/DNA nanohybrid

International Nuclear Information System (INIS)

Zuo Guifu; Wan Yizao; Meng Xianguang; Zhao Qing; Ren Kaijing; Jia Shiru; Wang Jiehua

2011-01-01

Research highlights: → A lamellar hydroxyapatite (HAp)/DNA nanohybrid was prepared as a novel gene delivering vector. → Gel electrophoresis analysis confirmed that the lamellar HAp could protect DNA from degradation of DNase I. → The protected DNA in the HAp/DNA nanohybrid could be recovered readily under acid conditions. - Abstract: Two-dimensional layered materials exhibit desired functionalities when being used as gene delivery materials. In this study, a novel gene delivering vector, lamellar hydroxyapatite (HAp)/DNA nanohybrid was prepared. The structure of HAp/DNA nanohybrid was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared (FT-IR) spectroscopy analysis revealed that ion-exchange occurred during the process. Gel electrophoresis analysis confirmed that the lamellar HAp could protect DNA from degradation of DNase I and the protected DNA could be recovered readily under acid conditions. Furthermore, the integrity of released DNA was confirmed by UV-vis spectra.

Radiation cured acrylonitrile--butadiene elastomers

International Nuclear Information System (INIS)

Eldred, R.J.

1976-01-01

In accordance with a preferred embodiment of this invention, the ultimate elongation of an electron beam radiation cured acrylonitrile-butadiene elastomer is significantly increased by the incorporation of a preferred noncrosslinking monomer, glycidyl methacrylate, in combination with the conventional crosslinking monomer, trimethylolpropanetrimethacrylate, prior to the radiation curing process

Direct Observation of the BCC (100) Plane in Thin Films of Sphere-forming Diblock Copolymers

Science.gov (United States)

Ji, Shengxiang; Nagpal, Umang; Liao, Wen; de Pablo, Juan; Nealey, Paul

2010-03-01

In sphere-forming diblock copolymers, periodic arrays of spheres are arranged in a body-centred cubic (BCC) lattice structure in bulk. However, in thin films different surface morphologies were observed as a function of the film thickness, and the transition from the hexagonal array to the BCC (110) arrangement of spheres on film surfaces was located with respect to the increase of the film thickness. Here we report the first direct observation of the BCC (100) plane in thin films of poly (styrene-b-methyl methacrylate) diblock copolymers on homogeneous substrates. By balancing the surface energies of both blocks, the lower energy BCC (100) plane corresponding to a square arrangement of half spheres, formed on film surfaces when the film thickness was commensurate with the spacing, L100, between (100) planes or greater than 2 L100. A hexagonal arrangement of spheres was only observed when the thickness was less than 2 L100 and incommensurate with 1 L100. Monte Carlo (MC) simulation confirmed our experimental observation and was used to investigate the transition of the arrangement of spheres as a function of the film thickness.

Shape Memory Polymer Composites of Poly(styrene-b-butadiene-b-styrene Copolymer/Liner Low Density Polyethylene/Fe3O4 Nanoparticles for Remote Activation

Directory of Open Access Journals (Sweden)

Yongkun Wang

2016-11-01

Full Text Available Magnetically sensitive shape memory poly(styrene-b-butadiene-b-styrene copolymer (SBS/liner low density polyethylene (LLDPE composites filled with various contents of Fe3O4 nanoparticles were prepared. The influence of the Fe3O4 nanoparticles content on the thermal properties, mechanical properties, fracture morphology, magnetic behavior, and shape memory effect of SBS/LLDPE/Fe3O4 composites was systematically studied in this paper. The results indicated that homogeneously dispersed Fe3O4 nanoparticles ensured the uniform heat generation and transfer in the alternating magnetic field, and endowed the SBS/LLDPE/Fe3O4 composites with an excellent magnetically responsive shape memory effect. When the shape memory composites were in the alternating magnetic field (f = 60 kHz, H = 21.21 kA·m−1, the best shape recovery ratio reached 99%, the shape retention ratio reached 99.4%, and the shape recovery speed increased significantly with the increment of Fe3O4 nanoparticles. It is anticipated that tagging products with this novel shape memory composite is helpful for the purpose of an intravascular delivery system in Micro-Electro-Mechanical System (MEMS devices.

EFFECT OF INCORPORATING EXPANDED POLYSTYRENE ...

African Journals Online (AJOL)

2012-11-03

Nov 3, 2012 ... Incorporating expanded polystyrene granules in concrete matrix can produce lightweight polystyrene aggregate concrete of ... structure. [1] reported that the standard workability tests are not suitable for the polystyrene aggregate concrete since they are sensitive to the unit weight of concrete. [2] made ...

Synthesis and self-assembly behavior of amphiphilic diblock copolymer dextran-block-poly(ε-caprolactone (DEX-b-PCL in aqueous media

Directory of Open Access Journals (Sweden)

2010-10-01

Full Text Available An amphiphilic diblock copolymer, dextran-block-poly(ε-caprolactone (DEX-b-PCL, with a series of welldefined chain lengths of each block was prepared by conjugating a dextran chain with a PCL block via aza-Michael addition reaction under mild conditions. For the dextran block, samples with relatively uniform molecular weight, 3.5 and 6.0 kDa, were used, and the PCL blocks were prepared via ring-opening polymerization at defined ratios of ε-caprolactone to initiator in order to give copolymers with mass fraction of dextran (fDEX ranging from 0.16 to 0.45. When these copolymers were allowed to self-assemble in aqueous solution, the morphology of assembled aggregates varied as a function of fDEX when characterized by transmission electron microscope (TEM, fluorescence microscope (FM and dynamic laser scattering (DLS. As fDEX decreases gradually from 0.45 to 0.16, the morphology of the copolymer assembly changes from spherical micelles to worm-like micelles and eventually to polymersomes, together with an increase in particle sizes.

Anatomical and Functional Results of Lamellar Macular Holes Surgery.

Science.gov (United States)

Papadopoulou, D; Donati, G; Mangioris, G; Pournaras, C J

2016-04-01

To determine the long-term surgical findings and outcomes after vitrectomy for symptomatic lamellar macular holes. We studied 28 patients with lamellar macular holes and central visual loss or distortion. All interventions were standard 25 G vitrectomy with membranectomy of the internal limiting membrane (ILM), peeling and gas tamponade with SF6 20 %. Operations were performed by a single experienced surgeon within the last 3 years. Best corrected visual acuity and optical coherence tomography appearance were determined preoperatively and postoperatively. Following the surgical procedure, all macular holes were closed; however, in 3 eyes, significant foveal thinning was associated with changes in the retinal pigment epithelium changes. The mean best-corrected visual acuity improved postoperatively in the majority of the patients (n: 21, mean 0.3 logMAR), stabilised in 4 patients and decreased in 3 patients (mean 0.4 logMAR). Spectral Domain-Optical coherence tomography (SD-OCT) showed resolution of the lamellar lesion and improved macular contour in all cases. We demonstrated improvement in postoperative vision and the anatomical reconstruction of the anatomical contour of the fovea in most eyes with symptomatic lamellar holes. These findings indicate that vitrectomy, membranectomy and ILM peeling with gas tamponade is a beneficial treatment of symptomatic lamellar macular holes. Georg Thieme Verlag KG Stuttgart · New York.

Structure of micelles formed by highly asymmetric polystyrene-b-polydimethylsiloxane and polystyrene-b-poly[5-(N,N-diethylamino)isoprene] diblock copolymers

Czech Academy of Sciences Publication Activity Database

Giacomelli, F. C.; Riegel, I. C.; Štěpánek, Petr; Petzhold, C. L.; Ninago, M. D.; Satti, A. J.; Ciolino, A. E.; Villar, M. A.; Schmidt, V.; Giacomelli, C.

2010-01-01

Roč. 26, č. 18 (2010), s. 14494-14501 ISSN 0743-7463 R&D Projects: GA ČR GA202/09/2078 Grant - others:AV ČR(CZ) ASCR/CONICET 2012CZ006 Institutional research plan: CEZ:AV0Z40500505 Keywords : dynamic light-scattering * block-copolymers * selective solvent Subject RIV: BO - Biophysics Impact factor: 4.269, year: 2010

Effect of plasticiser on properties of styrene-butadiene-styrene thermoplastic elastomers

International Nuclear Information System (INIS)

Norzalia, S.; Farid, A.S.; O'Brien, M.G.

1999-01-01

This study investigates the properties of plasticised styrene-butadiene-styrene thermoplastic elastomers for possible applications in pharmaceutical, medical and food industries. Unplasticised styrene-butadiene-styrene (USBS) materials: vector 8550-D and vector 4461-D, which are developmental materials introduced by Exxon, and blends of vector 8550-D with vector 4461-D were plasticised paraffinic type plasticisers plastol 172 and plastol 352. Shore A hardness, tensile stress at break, modulus at 100% strain, elongation at break and density values showed a decrease whereas flow properties such as melt flow index (MFI) increased considerably with increasing plasticiser concentration. The properties of the plasticised styrene-butadiene-styrene thermoplastic elastomers were compared to the USBS materials. (author)

Effect of reactive monomer on PS-b-P2VP film.

Science.gov (United States)

Kim, H J; Shin, D M

2014-08-01

Poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) lamellar film which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 52 kg/mol-b-57 kg/mol and PS-b-P2VP film with reactive monomer (RM257) were prepared for photonic gel films. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic moiety of PS-b-P2VP, were obtained by exposing the spin coated film under chloroform vapor. The lamellar films were quaternized with 5 wt% of iodomethane diluted by n-hexane. We reported about the influence of reactive monomer on those photonic gel films. Added reactive monomer photonic gel film had higher absorbance than pure photonic gel films. As a result the photonic gel film with RM had more clear color. The lamellar films were swollen by DI water, ethanol (aq) and calcium carbonate solution. The band gaps of the lamellar films were drastically shifted to longer wavelength swollen by calcium carbonate solution. And the lamellar films were shifted to shorter wave length swollen by ethanol. So each lamellar film showed different color.

Broadband pH-Sensing Organic Transistors with Polymeric Sensing Layers Featuring Liquid Crystal Microdomains Encapsulated by Di-Block Copolymer Chains.

Science.gov (United States)

Seo, Jooyeok; Song, Myeonghun; Jeong, Jaehoon; Nam, Sungho; Heo, Inseok; Park, Soo-Young; Kang, Inn-Kyu; Lee, Joon-Hyung; Kim, Hwajeong; Kim, Youngkyoo

2016-09-14

We report broadband pH-sensing organic field-effect transistors (OFETs) with the polymer-dispersed liquid crystal (PDLC) sensing layers. The PDLC layers are prepared by spin-coating using ethanol solutions containing 4-cyano-4'-pentyl-biphenyl (5CB) and a diblock copolymer (PAA-b-PCBOA) that consists of LC-philic block [poly(4-cyano-biphenyl-4-oxyundecyl acrylate) (PCBOA)] and acrylic acid block [poly(acrylic acid) (PAA)]. The spin-coated sensing layers feature of 5CB microdomains (pH with only small amounts (10-40 μL) of analyte solutions in both static and dynamic perfusion modes. The positive drain current change is measured for acidic solutions (pH pH > 7) result in the negative change of drain current. The drain current trend in the present PDLC-i-OFET devices is explained by the shrinking-expanding mechanism of the PAA chains in the diblock copolymer layers.

Influence of fall height on high impact polystyrene deformation and characteristics of drop weight test

Directory of Open Access Journals (Sweden)

Mizera Ales

2017-01-01

Full Text Available This study deals with high impact polystyrene (HIPS which was subjected the drop-weight test. HIPS is a polymer produced by the reaction between butadiene synthetic elastomer and styrene (5–14 % which contains the crystal polymer in certain amounts and is commonly used in mechanical engineering applications where machine parts are exposed to impact loading. The injection moulded HIPS samples were subjected the penetration test at different fall heights and the results were subsequently evaluated and discussed. It was found out that all fall heights are suitable for HIPS penetration, but the optimal one is 50 J because of the smallest variation range. Higher heights are not needed because of increasing power consumption of the test device. From the results, it is clear, that HIPS is not so highly impact resistant material as for example HDPE, because of that is this material suitable for applications where is not often exposed to too big impacts at high velocities.

Thermodynamic interactions of water-soluble homopolymers and double-hydrophilic diblock copolymer

International Nuclear Information System (INIS)

Yazici, D. Topaloglu; Askin, A.; Buetuen, V.

2008-01-01

Thermodynamic interaction parameters of water-soluble poly[2-(dimethylamino)ethyl methacrylate] (DMA) and poly[2-(N-morpholino)ethyl methacrylate] (MEMA) homopolymers and their diblock copolymer (DMA-MEMA) were investigated at the temperatures above their glass-transition temperatures (T g ) by inverse gas chromatography (IGC) method. Sorption thermodynamic parameters of some aliphatic, alicyclic and aromatic hydrocarbons, weight fraction activity coefficients, Flory-Huggins interaction parameters, and solubility parameters for hydrocarbons and polymers were calculated. It was observed that sorption thermodynamic parameters on (co)polymers depend on the molecular structures of hydrocarbons. Evaluating both the calculated values of the weight fraction activity coefficients and Flory-Huggins interaction parameters, the solving ability of the hydrocarbons for DMA, MEMA homopolymers, and DMA-MEMA diblock copolymer decreased in the following sequence: Aromatic > alicyclic > aliphatic hydrocarbons

First principles calculations of interstitial and lamellar rhenium nitrides

Energy Technology Data Exchange (ETDEWEB)

Soto, G., E-mail: gerardo@cnyn.unam.mx [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia, Km 107 Carretera Tijuana-Ensenada, Ensenada Baja California (Mexico); Tiznado, H.; Reyes, A.; Cruz, W. de la [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia, Km 107 Carretera Tijuana-Ensenada, Ensenada Baja California (Mexico)

2012-02-15

Highlights: Black-Right-Pointing-Pointer The possible structures of rhenium nitride as a function of composition are analyzed. Black-Right-Pointing-Pointer The alloying energy is favorable for rhenium nitride in lamellar arrangements. Black-Right-Pointing-Pointer The structures produced by magnetron sputtering are metastable variations. Black-Right-Pointing-Pointer The structures produced by high-pressure high-temperature are stable configurations. Black-Right-Pointing-Pointer The lamellar structures are a new category of interstitial dissolutions. - Abstract: We report here a systematic first principles study of two classes of variable-composition rhenium nitride: i, interstitial rhenium nitride as a solid solution and ii, rhenium nitride in lamellar structures. The compounds in class i are cubic and hexagonal close-packed rhenium phases, with nitrogen in the octahedral and tetrahedral interstices of the metal, and they are formed without changes to the structure, except for slight distortions of the unit cells. In the compounds in class ii, by contrast, the nitrogen inclusion provokes stacking faults in the parent metal structure. These faults create trigonal-prismatic sites where the nitrogen residence is energetically favored. This second class of compounds produces lamellar structures, where the nitrogen lamellas are inserted among multiple rhenium layers. The Re{sub 3}N and Re{sub 2}N phases produced recently by high-temperature and high-pressure synthesis belong to this class. The ratio of the nitrogen layers to the rhenium layers is given by the composition. While the first principle calculations point to higher stability for the lamellar structures as opposed to the interstitial phases, the experimental evidence presented here demonstrates that the interstitial classes are synthesizable by plasma methods. We conclude that rhenium nitrides possess polymorphism and that the two-dimensional lamellar structures might represent an emerging class of materials

First principles calculations of interstitial and lamellar rhenium nitrides

International Nuclear Information System (INIS)

Soto, G.; Tiznado, H.; Reyes, A.; Cruz, W. de la

2012-01-01

Highlights: ► The possible structures of rhenium nitride as a function of composition are analyzed. ► The alloying energy is favorable for rhenium nitride in lamellar arrangements. ► The structures produced by magnetron sputtering are metastable variations. ► The structures produced by high-pressure high-temperature are stable configurations. ► The lamellar structures are a new category of interstitial dissolutions. - Abstract: We report here a systematic first principles study of two classes of variable-composition rhenium nitride: i, interstitial rhenium nitride as a solid solution and ii, rhenium nitride in lamellar structures. The compounds in class i are cubic and hexagonal close-packed rhenium phases, with nitrogen in the octahedral and tetrahedral interstices of the metal, and they are formed without changes to the structure, except for slight distortions of the unit cells. In the compounds in class ii, by contrast, the nitrogen inclusion provokes stacking faults in the parent metal structure. These faults create trigonal-prismatic sites where the nitrogen residence is energetically favored. This second class of compounds produces lamellar structures, where the nitrogen lamellas are inserted among multiple rhenium layers. The Re 3 N and Re 2 N phases produced recently by high-temperature and high-pressure synthesis belong to this class. The ratio of the nitrogen layers to the rhenium layers is given by the composition. While the first principle calculations point to higher stability for the lamellar structures as opposed to the interstitial phases, the experimental evidence presented here demonstrates that the interstitial classes are synthesizable by plasma methods. We conclude that rhenium nitrides possess polymorphism and that the two-dimensional lamellar structures might represent an emerging class of materials within binary nitride chemistry.

Mechanisms of lamellar collagen formation in connective tissues.

Science.gov (United States)

Ghazanfari, Samaneh; Khademhosseini, Ali; Smit, Theodoor H

2016-08-01

The objective of tissue engineering is to regenerate functional tissues. Engineering functional tissues requires an understanding of the mechanisms that guide the formation and evolution of structure in the extracellular matrix (ECM). In particular, the three-dimensional (3D) collagen fiber arrangement is important as it is the key structural determinant that provides mechanical integrity and biological function. In this review, we survey the current knowledge on collagen organization mechanisms that can be applied to create well-structured functional lamellar tissues and in particular intervertebral disc and cornea. Thus far, the mechanisms behind the formation of cross-aligned collagen fibers in the lamellar structures is not fully understood. We start with cell-induced collagen alignment and strain-stabilization behavior mechanisms which can explain a single anisotropically aligned collagen fiber layer. These mechanisms may explain why there is anisotropy in a single layer in the first place. However, they cannot explain why a consecutive collagen layer is laid down with an alternating alignment. Therefore, we explored another mechanism, called liquid crystal phasing. While dense concentrations of collagen show such behavior, there is little evidence that the conditions for liquid crystal phasing are actually met in vivo. Instead, lysyl aldehyde-derived collagen cross-links have been found essential for correct lamellar matrix deposition. Furthermore, we suggest that supra-cellular (tissue-level) shear stress may be instrumental in the alignment of collagen fibers. Understanding the potential mechanisms behind the lamellar collagen structure in connective tissues will lead to further improvement of the regeneration strategies of functional complex lamellar tissues. Copyright © 2016 Elsevier Ltd. All rights reserved.

Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

Energy Technology Data Exchange (ETDEWEB)

Agrawal, Neha, E-mail: neha87bhu@gmail.com [Defence Material Store Research Development and Establishment (DMSRDE), DRDO, GT Road, Kanpur 208013, U.P (India); Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra (India); Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Mukhopadhyay, K.; Prasad, N. E. [Defence Material Store Research Development and Establishment (DMSRDE), DRDO, GT Road, Kanpur 208013, U.P (India); Gandhi, M. N.; Bhattacharyya, A. R. [Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra (India)

2016-05-06

Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS{sub 2}) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS{sub 2} and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS{sub 2} and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

International Nuclear Information System (INIS)

Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Mukhopadhyay, K.; Prasad, N. E.; Gandhi, M. N.; Bhattacharyya, A. R.

2016-01-01

Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS_2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS_2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS_2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

Science.gov (United States)

Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Gandhi, M. N.; Bhattacharyya, A. R.; Mukhopadhyay, K.; Prasad, N. E.

2016-05-01

Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

Au-coated 3-D nanoporous titania layer prepared using polystyrene-b-poly(2-vinylpyridine) block copolymer nanoparticles.

Science.gov (United States)

Shin, Won-Jeong; Basarir, Fevzihan; Yoon, Tae-Ho; Lee, Jae-Suk

2009-04-09

New nanoporous structures of Au-coated titania layers were prepared by using amphiphilic block copolymer nanoparticles as a template. A 3-D template composed of self-assembled quaternized polystyrene-b-poly(2-vinylpyridine) (Q-PS-b-P2VP) block copolymer nanoparticles below 100 nm was prepared. The core-shell-type nanoparticles were well ordered three-dimensionally using the vertical immersion method on the substrate. The polar solvents were added to the polymer solution to prevent particle merging at 40 degrees C when considering the interaction between polymer nanoparticles and solvents. Furthermore, Au-coated PS-b-P2VP nanoparticles were prepared using thiol-capped Au nanoparticles (3 nm). The 3-D arrays with Au-coated PS-b-P2VP nanoparticles as a template contributed to the preparation of the nanoporous Au-coated titania layer. Therefore, the nanoporous Au-coated titania layer was fabricated by removing PS-b-P2VP block copolymer nanoparticles by oxygen plasma etching.

Volume holographic storage and multiplexing in blends of PMMA and a block methacrylic azopolymer, using 488 nm light pulses in the range of 100 ms to 1 s

DEFF Research Database (Denmark)

Forcen, Patricia; Oriol, Luis; Sanchez, Carlos

2008-01-01

Blends of polymethylmethacrylate (PMMA) and diblock methacrylic azopolymers have been investigated for holographic storage with short light pulses. Transmission electron microscopy measurements show that the dilution of the block copolymer in PMMA changes the microstructure from a lamellar to a s...

Double-brush Langmuir-Blodgett monolayers of alpha-helical diblock copolypeptides

NARCIS (Netherlands)

Nguyen, Le-Thu T.; Vorenkamp, Eltjo J.; Daumont, Christophe J. M.; ten Brinke, Gerrit; Schouten, Arend J.; Vukovic, Ivana; Loos, Katja

2010-01-01

The synthesis of amphiphilic diblock copolypeptides consisting of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) and their monolayer behavior at the air-water interface have been studied.

Endothelial cell density after deep anterior lamellar keratoplasty (Melles technique)

NARCIS (Netherlands)

Van Dooren, BTH; Mulder, PGH; Nieuwendaal, CP; Beekhuis, WH; Melles, GRJ

PURPOSE: To measure the recipient endothelial cell loss after the Melles technique for deep anterior lamellar keratoplasty. METHODS: In 21 eyes of 21 patients, a deep anterior lamellar keratoplasty procedure was performed. Before surgery and at 6, 12, and 24 months after surgery, specular microscopy

Does lamellar surgery for keratoconus experience the popularity it deserves?

Science.gov (United States)

Wisse, Robert P L; van den Hoven, Célinde M L; Van der Lelij, Allegonda

2014-08-01

To analyse developments in surgical treatment for keratoconus (KC) by assessing rates and types of corneal surgery from 2005 to 2010. The Dutch Transplantation Foundation supplied data on all keratoplasty procedures for KC performed from 2005 to 2010 in the Netherlands. Registration was carried out by the eyebank at allocation and by the surgeon at the time of surgery. The type of surgery was categorized as either a penetrating or a lamellar procedure. Five hundred and seventy-five anonymized records were received, with excellent data completion (99%). Patients undergoing penetrating surgery had on average a lower visual acuity, higher k-readings and were slightly older compared with the lamellar group. A previous corneal hydrops was recorded for 19.1% of patients. Regular penetrating keratoplasty decreased in popularity from 79.7% in 2005 to 43.7% in 2010, due to the increased rate of lamellar surgery (42.5% in 2010) and 'mushroom' penetrating keratoplasty (13.8% in 2010). When hydrops cases were excluded, popularity became equal (47.6% penetrating versus 52.4% lamellar surgery, in 2010). Lamellar surgery is gaining in popularity, although regular penetrating keratoplasty is still the more commonly performed procedure. Only when hydrops cases are excluded do transplant rates become comparable. © 2013 Acta Ophthalmologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Vibrational investigation on FT-IR and FT-Raman spectra, IR intensity, Raman activity, peak resemblance, ideal estimation, standard deviation of computed frequencies analyses and electronic structure on 3-methyl-1,2-butadiene using HF and DFT (LSDA/B3LYP/B3PW91) calculations.

Science.gov (United States)

Ramalingam, S; Jayaprakash, A; Mohan, S; Karabacak, M

2011-11-01

FT-IR and FT-Raman (4000-100 cm(-1)) spectral measurements of 3-methyl-1,2-butadiene (3M12B) have been attempted in the present work. Ab-initio HF and DFT (LSDA/B3LYP/B3PW91) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, IR intensities and Raman activities. Complete vibrational assignments on the observed spectra are made with vibrational frequencies obtained by HF and DFT (LSDA/B3LYP/B3PW91) at 6-31G(d,p) and 6-311G(d,p) basis sets. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The potential energy distribution (PED) corresponding to each of the observed frequencies are calculated which confirms the reliability and precision of the assignment and analysis of the vibrational fundamentals modes. The oscillation of vibrational frequencies of butadiene due to the couple of methyl group is also discussed. A study on the electronic properties such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties of the title compound at different temperatures reveal the correlations between standard heat capacities (C) standard entropies (S), and standard enthalpy changes (H). Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Structural transition with thickness in films of poly-(styrene-b-2vinylpyridine) (PS-b-P2VP) diblock copolymer/homopolymer blends

Science.gov (United States)

Mishra, Vindhya; Kramer, Edward; Hur, Su-Mi; Fredrickson, Glenn; Sprung, Michael

2009-03-01

In multilayer thin films of spherical morphology block copolymers, the surface layers prefer hexagonal symmetry while the inner layers prefer BCC. Thin films with spherical morphology of PS-b-P2VP blends with short homopolymer polystyrene (hPS) chains have an HCP structure up to a thickness n* at which there is a transition to a face centered orthorhombic structure. Using grazing incidence small angle X-ray scattering and transmission electron microscopy we show that that n* increases from 5 to 9 with increase in hPS from 0 to 12 vol%. For thicknesses just below n* the HCP and FCO structures coexist, but on long annealing HCP prevails. We hypothesize that the PS segregates to the interstices in the HCP structure reducing the stretching of the PS blocks and the free energy penalty of HCP versus BCC inner layers. Self consistent field theoretic simulations are being carried out to see if this idea is correct.

Endothelial cell density after deep anterior lamellar keratoplasty (Melles technique)

NARCIS (Netherlands)

van Dooren, Bart T. H.; Mulder, Paul G. H.; Nieuwendaal, Carla P.; Beekhuis, W. Houdijn; Melles, Gerrit R. J.

2004-01-01

To measure the recipient endothelial cell loss after the Melles technique for deep anterior lamellar keratoplasty. In 21 eyes of 21 patients, a deep anterior lamellar keratoplasty procedure was performed. Before surgery and at 6, 12, and 24 months after surgery, specular microscopy was performed to

Precipitation kinetics of lamellar (γ) laths in a TiAl-base alloy

International Nuclear Information System (INIS)

Zhang, W.J.; Francesconi, L.; Evangelista, E.

1997-01-01

Titanium aluminide is a candidate material for high temperature applications. Although different types of microstructure have been produced in TiAl-base alloys, the fully-lamellar structure is currently regarded as the most attractive. This kind of microstructure can be characterized by the factors, namely, colony size, lamellar interspacing, the existence of Widmanstatten (secondary) laths, and the type of grain boundaries (smooth or interlocking). The objective of this paper is to examine the nucleation and growth kinetics of γ lamellar laths during continuous and isothermal cooling. These data are expected to benefit the understanding of the transformation mechanism and the design of lamellar TiAl microstructure for industrial application

Structure-rheology relationship in a sheared lamellar fluid.

Science.gov (United States)

Jaju, S J; Kumaran, V

2016-03-01

The structure-rheology relationship in the shear alignment of a lamellar fluid is studied using a mesoscale model which provides access to the lamellar configurations and the rheology. Based on the equations and free energy functional, the complete set of dimensionless groups that characterize the system are the Reynolds number (ργL(2)/μ), the Schmidt number (μ/ρD), the Ericksen number (μγ/B), the interface sharpness parameter r, the ratio of the viscosities of the hydrophilic and hydrophobic parts μ(r), and the ratio of the system size and layer spacing (L/λ). Here, ρ and μ are the fluid density and average viscosity, γ is the applied strain rate, D is the coefficient of diffusion, B is the compression modulus, μ(r) is the maximum difference in the viscosity of the hydrophilic and hydrophobic parts divided by the average viscosity, and L is the system size in the cross-stream direction. The lattice Boltzmann method is used to solve the concentration and momentum equations for a two dimensional system of moderate size (L/λ=32) and for a low Reynolds number, and the other parameters are systematically varied to examine the qualitative features of the structure and viscosity evolution in different regimes. At low Schmidt numbers where mass diffusion is faster than momentum diffusion, there is fast local formation of randomly aligned domains with "grain boundaries," which are rotated by the shear flow to align along the extensional axis as time increases. This configuration offers a high resistance to flow, and the layers do not align in the flow direction even after 1000 strain units, resulting in a viscosity higher than that for an aligned lamellar phase. At high Schmidt numbers where momentum diffusion is fast, the shear flow disrupts layers before they are fully formed by diffusion, and alignment takes place by the breakage and reformation of layers by shear, resulting in defects (edge dislocations) embedded in a background of nearly aligned layers

Self-assembling of poly(ε-caprolactone)-b-poly(ethylene oxide) diblock copolymers in aqueous solution and at the silica-water interface

International Nuclear Information System (INIS)

Leyh, B.; Vangeyte, P.; Heinrich, M.; Auvray, L.; De Clercq, C.; Jerome, R.

2004-01-01

Small-angle neutron scattering is used to investigate the self-assembling behaviour of poly(ε-caprolactone)-b-poly(ethylene oxide) diblock copolymers with various block lengths (i) in aqueous solution, (ii) in aqueous solution with the addition of sodium dodecyl sulphate (SDS) and (iii) at the silica-water interface. Micelles are observed under our experimental conditions due to the very small critical micellar concentration of these copolymers (0.01 g/l). The poly(ε-caprolactone) core is surrounded by a poly(ethylene oxide) corona. The micellar form factors have been measured at low copolymer concentrations (0.2 wt%) under selected contrast matching conditions. The data have been fitted to various analytical models to extract the micellar core and corona sizes. SDS is shown to induce partial micelle disruption together with an increase of the poly(ethylene oxide) corona extension from 25% (without SDS) to 70% (with SDS) of a completely extended PEO 114 chain. Our data at the silica-water interface are compatible with the adsorption of micelles

Self-Assembling Diblock Copolymers of Poly[N-(2-hydroxypropyl)methacrylamide] and a β-Sheet Peptide

Science.gov (United States)

Radu, Larisa Cristina; Yang, Jiyuan

2015-01-01

The self-assembly of hybrid diblock copolymers composed of poly(HPMA) and β-sheet peptide P11 (CH3CO-QQRFQWQFEQQ-NH2) blocks was investigated. Copolymers were synthesized via thiol-maleimide coupling reaction, by conjugation of semitelechelic poly(HPMA)-SH with maleimide-modified β-sheet peptide. As expected, CD and CR binding studies showed that the peptide block imposed its β-sheet structural arrangement on the structure of diblock copolymers. TEM and AFM proved that peptide and these copolymers had the ability to self-assemble into fibrils. PMID:18855948

Effects of Different Types of Clays and Maleic Anhydride Modified Polystyrene on Polystyrene/Clay Nanocomposites

Directory of Open Access Journals (Sweden)

M. Mehrabzadeh

2013-01-01

Full Text Available Polymer/clay nanocomposites are considered as a new subject of research in Iran and the world. Addition of a minimum amount of clay (2-5wt% can improve the mechanical properties, enhance barrier properties and reduce flammability dramatically. Polystyrene (PS exhibits high strength, high modulus and excellent dimensional stability, but it has poor ductility, elongation, and flexural modulus. By incorporating clay into polystyrene these properties can be improved. In this study preparation of polystyrene/clay nanocomposite, effects of different types of clays (Cloisite 10A andNanomer I.30TC and maleic anhydride modified polystyrene on mechanical properties of the prepared polystyrene/clay nanocomposites were evaluated. Samples were prepared by a twin screw extruder. Transmission electron microscopy (TEM and X-ray diffraction (XRD techniques were employed to evaluate the extent of intercalation and exfoliation of silicate layers in the nanocomposites. Mechanical tests show that by addition of clay and maleic anhydride modified polystyrene the flexural modulus (~30% and elongation-at-break (~40% of prepared nanocomposites have been improved. XRD and TEM results show that nanocomposite have an intercalated structure with ability to change to further exfoliation structure.

Investigation of surface halide modification of nitrile butadiene rubber

Science.gov (United States)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

Solid polystyrene and deuterated polystyrene light output response to fast neutrons

International Nuclear Information System (INIS)

Simpson, R.; Danly, C.; Merrill, F. E.; Volegov, P. L.; Wilde, C.; Glebov, V. Yu.; Hurlbut, C.

2016-01-01

The Neutron Imaging System has proven to be an important diagnostic in studying DT implosion characteristics at the National Ignition Facility. The current system depends on a polystyrene scintillating fiber array, which detects fusion neutrons born in the DT hotspot as well as neutrons that have scattered to lower energies in the surrounding cold fuel. Increasing neutron yields at NIF, as well as a desire to resolve three-dimensional information about the fuel assembly, have provided the impetus to build and install two additional next-generation neutron imaging systems. We are currently investigating a novel neutron imaging system that will utilize a deuterated polystyrene (CD) fiber array instead of standard hydrogen-based polystyrene (CH). Studies of deuterated xylene or deuterated benzene liquid scintillator show an improvement in imaging resolution by a factor of two [L. Disdier et al., Rev. Sci. Instrum. 75, 2134 (2004)], but also a reduction in light output [V. Bildstein et al., Nucl. Instrum. Methods Phys. Res., Sect. A 729, 188 (2013); M. I. Ojaruega, Ph.D. thesis, University of Michigan, 2009; M. T. Febbraro, Ph.D. thesis, University of Michigan, 2014] as compared to standard plastic. Tests of the relative light output of deuterated polystyrene and standard polystyrene were completed using 14 MeV fusion neutrons generated through implosions of deuterium-tritium filled capsules at the OMEGA laser facility. In addition, we collected data of the relative response of these two scintillators to a wide energy range of neutrons (1-800 MeV) at the Weapons Neutrons Research Facility. Results of these measurements are presented.

Solid polystyrene and deuterated polystyrene light output response to fast neutrons

Energy Technology Data Exchange (ETDEWEB)

Simpson, R., E-mail: raspberry@lanl.gov; Danly, C.; Merrill, F. E.; Volegov, P. L.; Wilde, C. [Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Glebov, V. Yu. [Laboratory for Laser Energetics, Rochester, New York 14623 (United States); Hurlbut, C. [Eljen Technology, Sweetwater, Texas 79556 (United States)

2016-04-15

The Neutron Imaging System has proven to be an important diagnostic in studying DT implosion characteristics at the National Ignition Facility. The current system depends on a polystyrene scintillating fiber array, which detects fusion neutrons born in the DT hotspot as well as neutrons that have scattered to lower energies in the surrounding cold fuel. Increasing neutron yields at NIF, as well as a desire to resolve three-dimensional information about the fuel assembly, have provided the impetus to build and install two additional next-generation neutron imaging systems. We are currently investigating a novel neutron imaging system that will utilize a deuterated polystyrene (CD) fiber array instead of standard hydrogen-based polystyrene (CH). Studies of deuterated xylene or deuterated benzene liquid scintillator show an improvement in imaging resolution by a factor of two [L. Disdier et al., Rev. Sci. Instrum. 75, 2134 (2004)], but also a reduction in light output [V. Bildstein et al., Nucl. Instrum. Methods Phys. Res., Sect. A 729, 188 (2013); M. I. Ojaruega, Ph.D. thesis, University of Michigan, 2009; M. T. Febbraro, Ph.D. thesis, University of Michigan, 2014] as compared to standard plastic. Tests of the relative light output of deuterated polystyrene and standard polystyrene were completed using 14 MeV fusion neutrons generated through implosions of deuterium-tritium filled capsules at the OMEGA laser facility. In addition, we collected data of the relative response of these two scintillators to a wide energy range of neutrons (1-800 MeV) at the Weapons Neutrons Research Facility. Results of these measurements are presented.

Laser thermokeratoplasty after lamellar corneal cutting.

Science.gov (United States)

Ismail, M M; Pérez-Santonja, J J; Alió, J L

1999-02-01

To evaluate the effect of laser thermokeratoplasty (LTK) in eyes that previously had a lamellar corneal cut. University of Al-Azhar, Cairo, Egypt, and Instituto Oftalmológico de Alicante, Spain. In 15 eyes (10 patients), noncontact LTK was applied 6 to 8 weeks after a lamellar corneal cut had been made. Central pachymetry, keratometry, and videokeratography were performed and uncorrected visual acuity, best spectacle-corrected visual acuity (BSCVA), and manifest and cycloplegic refractions measured before and 1, 6, 12, and 18 months after LTK. Mean follow-up was 19.13 months. Mean refraction was +5.93 diopters (D) +/- 1.9 (SD) before LTK and -0.43 +/- 1.5 D at 1 month, +1.63 +/- 1.6 D at 6 months, 1.91 +/- 1.41 at 12 months, and +2.01 +/- 1.5 D at the end of the study. Total regression did not occur in any case. Mean BSCVA before LTK was 0.66 +/- 0.2, and spontaneous visual acuity at the end of the study was 0.58 +/- 0.18. No patient lost any lines of preoperative BSCVA. There was no significant difference between the results at 12 months and at the end of the study. Corneal lamellar cutting appeared to improve the magnitude of the refractive effect of noncontact LTK and to decrease the amount of regression.

Square and Rectangular Arrays from Directed Assembly of Sphere-forming Diblock Copolymers in Thin Films

Science.gov (United States)

Ji, Shengxiang; Nagpal, Umang; Liao, Wen; de Pablo, Juan; Nealey, Paul

2010-03-01

Patterns of square and rectangular arrays with nanoscale dimensions are scientifically and technologically important. Fabrication of square array patterns in thin films has been demonstrated by directed assembly of cylinder-forming diblock copolymers on chemically patterned substrates, supramolecular assembly of diblock copolymers, and self-assembly of triblock terpolymers. However, a macroscopic area of square array patterns with long-range order has not been achieved, and the fabrication of rectangular arrays has not been reported so far. Here we report a facile approach for fabricating patterns of square and rectangular arrays by directing the assembly of sphere-forming diblock copolymers on chemically patterned substrates. On stripe patterns, a square arrangement of half spheres, corresponding to the (100) plane of the body-centred cubic (BCC) lattice, formed on film surfaces. When the underlying pattern periods mismatched with the copolymer period, the square pattern could be stretched (up to ˜60%) or compressed (˜15%) to form rectangular arrays. Monte Carlo simulations have been further used to verify the experimental results and the 3-dimensional arrangements of spheres.

Network structure control of binary mixed langmuir monolayers of homo-PS and PS-b-P2VP.

Science.gov (United States)

Wen, Gangyao

2010-03-25

Our recent work showed there existed a composition window for mixed Langmuir monolayers of homopolystyrene (h-PS) and a symmetric diblock copolymer polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) to form necklace-network structures at the air/water interface. In order to study further the possible mechanism and control the network structure (i.e., surface coverage and nanoaggregate diameter), effects of spreading solution concentration and volume, subphase temperature, and transfer pressure on the network structure were studied by the Langmuir monolayer technique and tapping mode atomic force microscopy. With the increase of transfer pressure, there existed a novel nonlinear behavior for the nanoaggregate diameter first to increase, then to decrease, and finally to increase again, while the surface coverage tended to increase step by step. Moreover, with the elevation of temperature, chain motion between the adjoining nanoaggregates tended to be improved and thus the nanoaggregate diameter tended to be more uniform.

Synthesis and conformational characterization of functional di-block copolymer brushes for microarray technology

Energy Technology Data Exchange (ETDEWEB)

Di Carlo, Gabriele; Damin, Francesco [Institute of Chemistry of Molecular Recognition, National Research Council of Italy, Via M. Bianco 9, 20131 Milano (Italy); Armelao, Lidia [ISTM-CNR and INSTM, Department of Chemistry, University of Padova, Via F. Marzolo 1, 35131 Padova (Italy); Maccato, Chiara [Department of Chemistry and INSTM, University of Padova, Via F. Marzolo 1, 35131 Padova (Italy); Unlu, Selim [Department of Electrical and Computer Engineering, Boston University, St. Mary Street 8, Boston, MA 02215 (United States); Department of Biomedical Engineering, Boston University, St. Mary Street 8, Boston, MA 02215 (United States); Spuhler, Philipp S. [Department of Biomedical Engineering, Boston University, St. Mary Street 8, Boston, MA 02215 (United States); Chiari, Marcella, E-mail: marcella.chiari@icrm.cnr.it [Institute of Chemistry of Molecular Recognition, National Research Council of Italy, Via M. Bianco 9, 20131 Milano (Italy)

2012-02-01

Surface initiated polymerization (SIP) coupled with reversible addition-fragmentation chain transfer polymerization (RAFT) was used to functionalize microarray glass slides with block polymer brushes. N,N-dimethylacrylamide (DMA) and N-acryloyloxysuccinimide (NAS) (graft-poly[DMA-b-(DMA-co-NAS)]) brushes, with di-block architecture, were prepared from a novel RAFT chain transfer agent bearing a silanating moiety (RAFT silane) directly anchored onto the glass surfaces. Conformational characterization of the coatings was performed by Self Spectral Interference Fluorescence Microscopy (SSFM), an innovative technique that describes the location of a fluorescent DNA molecule relative to a surface with sub-nanometer accuracy. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) were used to characterize the coatings composition and morphology.

Synthesis and conformational characterization of functional di-block copolymer brushes for microarray technology

International Nuclear Information System (INIS)

Di Carlo, Gabriele; Damin, Francesco; Armelao, Lidia; Maccato, Chiara; Unlu, Selim; Spuhler, Philipp S.; Chiari, Marcella

2012-01-01

Surface initiated polymerization (SIP) coupled with reversible addition-fragmentation chain transfer polymerization (RAFT) was used to functionalize microarray glass slides with block polymer brushes. N,N-dimethylacrylamide (DMA) and N-acryloyloxysuccinimide (NAS) (graft-poly[DMA-b-(DMA-co-NAS)]) brushes, with di-block architecture, were prepared from a novel RAFT chain transfer agent bearing a silanating moiety (RAFT silane) directly anchored onto the glass surfaces. Conformational characterization of the coatings was performed by Self Spectral Interference Fluorescence Microscopy (SSFM), an innovative technique that describes the location of a fluorescent DNA molecule relative to a surface with sub-nanometer accuracy. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) were used to characterize the coatings composition and morphology.

Transition behavior of asymmetric polystyrene-b-poly(2-vinylpyridine) films: A stable hexagonally modulated layer structure

Energy Technology Data Exchange (ETDEWEB)

Park, Sungmin; Koo, Kyosung; Kim, Kyunginn; Ahn, Hyungju; Lee, Byeongdu; Park, Cheolmin; Ryu, Du Yeol

2015-03-09

The phase transitions in the films of an asymmetric polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) were investigated by grazing incidence small-angle X-ray scattering (GISAXS) and transmission electron microscopy (TEM). Compared with the sequential transitions in the bulk, hexagonally perforated layer (HPL) – gyroid (GYR) – disorder (DIS) upon heating, the transitions in film geometry were dramatically changed with decreasing thickness due to the growing preferential interactions from substrate, resulting in a thickness-dependent transition diagram including four different morphologies of hexagonally modulated layer (HML), coexisting (HML and GYR), GYR, and DIS. Particularly in the films ≤10Lo, where Lo is d-spacing at 150 °C, a stable HML structure was identified even above the order-to-disorder transition (ODT) temperature of the bulk, which was attributed to the suppressed compositional fluctuations by the enhanced substrate interactions.

Simulative calculation of bromo-polystyrene mechanical properties

CERN Document Server

Wang Chao; Tang Yong Jian

2002-01-01

The non-crystal model of polystyrene and bromo-polystyrene was established with the help of simulative software in the computer. DREIDING was chosen as force field and its parameters is modified according to the published data. Based on the calculation results and other published data the mechanism properties of polystyrene and bromo-polystyrene, such as bulk module, Yong's module and Poisson's ratios, were discussed

Microelectrode Arrays and the Use of PEG-Functionalized Diblock Copolymer Coatings

Directory of Open Access Journals (Sweden)

Sakshi Uppal

2014-09-01

Full Text Available PEG-modified diblock copolymer surfaces have been examined for their compatibility with microelectrode array based analytical methods. The use of PEG-modified polymer surfaces on the arrays was initially problematic because the redox couples used in the experiments were adsorbed by the polymer. This led the current measured by cyclic voltammetry for the redox couple to be unstable and increase with time. However, two key findings allow the experiments to be successful. First, after multiple cyclic voltammograms the current associated with the redox couple does stabilize so that a good baseline current can be established. Second, the rate at which the current stabilizes is consistent every time a particular coated array is used. Hence, multiple analytical experiments can be conducted on an array coated with a PEG-modified diblock copolymer and the data obtained is comparable as long as the data for each experiment is collected at a consistent time point.

Synthesis and immobilization of polystyreneb-polyvinyltriethoxysilane micelles

KAUST Repository

Zhu, Saisai

2018-01-31

Diblock copolymers polystyrene-block-polyvinyltriethoxysilane (PS-b-PVTES) were synthesized via atom transfer radical polymerization (ATRP), which self-assembled into spherical micelles in solvent of THF-methanol mixtures. The self-assembled micelles were immobilized by cross-linking reaction of VTES in a shell layer of micelles. The chemical structures of block copolymers and morphology of micelles were characterized in detail. It was found that the size of immobilized micelles was strongly affected by the copolymer concentration, composition of mixture solvent, and block ratios.

Solvothermal Vapor Annealing of Lamellar Poly(styrene)-block-poly(d,l-lactide) Block Copolymer Thin Films for Directed Self-Assembly Application.

Science.gov (United States)

Cummins, Cian; Mokarian-Tabari, Parvaneh; Andreazza, Pascal; Sinturel, Christophe; Morris, Michael A

2016-03-01

Solvothermal vapor annealing (STVA) was employed to induce microphase separation in a lamellar forming block copolymer (BCP) thin film containing a readily degradable block. Directed self-assembly of poly(styrene)-block-poly(d,l-lactide) (PS-b-PLA) BCP films using topographically patterned silicon nitride was demonstrated with alignment over macroscopic areas. Interestingly, we observed lamellar patterns aligned parallel as well as perpendicular (perpendicular microdomains to substrate in both cases) to the topography of the graphoepitaxial guiding patterns. PS-b-PLA BCP microphase separated with a high degree of order in an atmosphere of tetrahydrofuran (THF) at an elevated vapor pressure (at approximately 40-60 °C). Grazing incidence small-angle X-ray scattering (GISAXS) measurements of PS-b-PLA films reveal the through-film uniformity of perpendicular microdomains after STVA. Perpendicular lamellar orientation was observed on both hydrophilic and relatively hydrophobic surfaces with a domain spacing (L0) of ∼32.5 nm. The rapid removal of the PLA microdomains is demonstrated using a mild basic solution for the development of a well-defined PS mask template. GISAXS data reveal the through-film uniformity is retained following wet etching. The experimental results in this article demonstrate highly oriented PS-b-PLA microdomains after a short annealing period and facile PLA removal to form porous on-chip etch masks for nanolithography application.

Insertion of anisotropic particles in lamellar surfactant phases

International Nuclear Information System (INIS)

Grillo, Isabelle

1998-01-01

We search for the interactions governing the possibility to mix organic and inorganic colloids. We use laponite, a synthetic anionic clay, made of 30 nm diameter and 1 nm thickness anisotropic disks. Three surfactant Systems, an anionic one (AOT), a cationic one (DDAB) and a nonionic one (C_1_2E_5) investigate three different cases of interaction forces. We establish experimentally the equilibrium phase diagrams and characterise the structure of these ternary Systems by SANS and SAXS experiments. We quantify the adsorption. An AOT bilayer surround the particle edges; an almost complete bilayer of DDAB and C_1_2E_5 is formed on the basal faces. SANS contrast variation experiments under controlled conditions along the adsorption isotherm of C_1_2E_5 allow to determine the average thickness of the adsorbed surfactant layer. In the monophasic lamellar domain, the particles stay between the membranes, when the spacing is larger than the particle thickness. In the biphasic domain, dense clay aggregates are in equilibrium with a lamellar phase, containing few amount of particles. They enter in the AOT bilayers when the space between the bilayers are smaller than 8 A. From the phase diagram and interaction forces study, three conditions of stability emerge: - an osmotic one: the osmotic lamellar pressure is higher or equal to the colloidal one. - an energetic one: the interaction energy between a particle and the surfactant bilayer is close to the particle energy in aqueous suspension. - an entropic one: particles should not inhibit the stabilising fluctuations of the lamellar phase. (author) [fr

Fabrication of Two-Dimensional Arrays of Diameter-Tunable PS-b-P2VP Nanowires at the Air/Water Interface.

Science.gov (United States)

Zhao, Xingjuan; Yu, Xiaoli; Lee, Yong-Ill; Liu, Hong-Guo

2016-11-15

Composite thin films with well-defined and parallel nanowires were fabricated from the binary blends of a diblock copolymer polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and several homopolystyrenes (h-PSs) at the air/liquid interface through a facile technique, which involves solution self-assembly, interface adsorption, and further self-organization processes. It was confirmed that the nanowires that appeared at the air/water interface came from the cylindrical micelles formed in solution. Interestingly, the diameters of the nanowires are uniform and can be tuned precisely from 45 to 247 nm by incorporating the h-PS molecules into the micellar core. This parallel alignment of the nanowires has potential applications in optical devices and enables the nanowires to be used as templates to prepare functional nanostructures. The extent to which h-PS molecules with different molecular weights are able to influence the diameter control of the nanowires was also systematically investigated.

Reversible addition-fragmentation chain transfer polymerization of 2-chloro-1,3-butadiene

OpenAIRE

Pullan, Nikki; Liu, Max; Topham, Paul D.

2013-01-01

Controlled polymerization of 2-chloro-1,3-butadiene using reversible addition–fragmentation chain transfer (RAFT) polymerization has been demonstrated for the first time. 2-Chloro-1,3-butadiene, more commonly known as chloroprene, has significant industrial relevance as a crosslinked rubber, with uses ranging from adhesives to integral automotive components. However, problems surrounding the inherent toxicity of the lifecycle of the thiourea-vulcanized rubber have led to the need for control ...

Review of old chemistry and new catalytic advances in the on-purpose synthesis of butadiene.

Science.gov (United States)

Makshina, Ekaterina V; Dusselier, Michiel; Janssens, Wout; Degrève, Jan; Jacobs, Pierre A; Sels, Bert F

2014-11-21

Increasing demand for renewable feedstock-based chemicals is driving the interest of both academic and industrial research to substitute petrochemicals with renewable chemicals from biomass-derived resources. The search towards novel platform chemicals is challenging and rewarding, but the main research activities are concentrated on finding efficient pathways to produce familiar drop-in chemicals and polymer building blocks. A diversity of industrially important monomers like alkenes, conjugated dienes, unsaturated carboxylic acids and aromatic compounds are thus targeted from renewable feedstock. In this context, on-purpose production of 1,3-butadiene from biomass-derived feedstock is an interesting example as its production is under pressure by uncertainty of the conventional fossil feedstock. Ethanol, obtained via fermentation or (biomass-generated) syngas, can be converted to butadiene, although there is no large commercial activity today. Though practised on a large scale in the beginning of the 20th century, there is a growing worldwide renewed interest in the butadiene-from-ethanol route. An alternative route to produce butadiene from biomass is through direct carbohydrate and gas fermentation or indirectly via the dehydration of butanediols. This review starts with a brief discussion on the different feedstock possibilities to produce butadiene, followed by a comprehensive summary of the current state of knowledge regarding advances and achievements in the field of the chemocatalytic conversion of ethanol and butanediols to butadiene, including thermodynamics and kinetic aspects of the reactions with discussions on the reaction pathways and the type of catalysts developed.

Color tuning of photonic gel films by UV irradiation

Science.gov (United States)

Shin, Sung Eui; Kim, Su Young; Shin, Dong Myung

2010-02-01

Block copolymers have drawn increasing attention for fabricating functional nanomaterials due to their properties of self-assembly. In particular, photonic crystals hold promise for multiple optical applications. We prepared 1D photonic crystals with polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) lamellar films which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 57 kg /mol-b-57 kg/mol. The lamellar stacks, which are alternating layers of hydrophilic and hydrophobic moiety of PS-b-P2VP, are obtained by exposing the spin coated film under chloroform vapor. The band gaps of the lamellar films interestingly varied after immersion into the quaternizing solvents containing 5wt% of iodomethane solubilized in n-hexane. We demonstrate about the influence of UV light on those photonic gel films. To study of different properties of films, UV-visible absorption spectra were measured as a different UV irradiation time at swollen films with distilled water. The UV-visible maximum absorption spectra shifted by UV irradiation time. Dependent on the time of UV irradiations, we can change the photonic band gap.

Freezing polystyrene-b-poly(2-vinylpyridine) micelle nanoparticles with different nanostructures and sizes.

Science.gov (United States)

Fan, Hailong; Jin, Zhaoxia

2014-04-28

Herein we report how to control the nanostructures and sizes of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) nanoparticles via manipulating freezing in solvent-exchange. By characterizing and analyzing the distinct structural features of the obtained nanoparticles, we recognized that micelle self-assembly happens in the precipitation of PS-b-P2VP when water is added into the block copolymer (BCP) solution. Solvent properties significantly influence micelle types that are vesicles in acetone/H2O and spherical micelles in tetrahydrofuran/H2O, respectively, thus further inducing different frozen nanostructures of the obtained nanoparticles, onion-like in acetone/H2O and large compound micelles in tetrahydrofuran/H2O. By changing the concentration of the block copolymers and the Vsolvent/VH2O ratio to modify the freezing stage at which block copolymer micelles are frozen, we can further control the size of the nanoparticles. Moreover, small molecules (phosphotungstic acid, pyrene, 1-pyrenebutyric acid) can be trapped into the block copolymer nanoparticles via the freezing process. Their distribution in the nanoparticles relies not only on the solvent property, but also on their interactions with block copolymers. The hybrid nanoparticles with ordered distribution of small molecules can be further changed to partially-void nanoparticles. Our study demonstrated that manipulating the freezing of block copolymers in the solvent exchange process is a simple and controllable fabrication method to generate BCP nanoparticles with different architectures.

On the catalytic gas phase oxidation of butadiene to furan

Energy Technology Data Exchange (ETDEWEB)

Kubias, B.; Rodemerck, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany); Ritschl, F.; Meisel, M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Chemie

1998-12-31

Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)

Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends

Energy Technology Data Exchange (ETDEWEB)

Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi; So, Soonyong; Bates, Frank S.; Lodge, Timothy P. (UMM)

2016-11-21

We examine the relationship between structure and ionic conductivity in salt-containing ternary polymer blends that exhibit various microstructured morphologies, including lamellae, a hexagonal phase, and a bicontinuous microemulsion, as well as the disordered phase. These blends consist of polystyrene (PS, M_n ≈ 600 g/mol) and poly(ethylene oxide) (PEO, M_n ≈ 400 g/mol) homopolymers, a nearly symmetric PS–PEO block copolymer (M_n ≈ 4700 g/mol), and lithium bis(trifluoromethane)sulfonamide (LiTFSI). These pseudoternary blends exhibit phase behavior that parallels that of well-studied ternary polymer blends consisting of A and B homopolymers compatibilized by an AB diblock copolymer. The utility of this framework is that all blends have nominally the same number of ethylene oxide, styrene, Li⁺, and TFSI– units, yet can exhibit a variety of microstructures depending on the relative ratio of the homopolymers to the block copolymer. For the systems studied, the ratio r = [Li⁺]/[EO] is maintained at 0.06, and the volume fraction of PS homopolymer is kept equal to that of PEO homopolymer plus salt. The total volume fraction of homopolymer is varied from 0 to 0.70. When heated through the order–disorder transition, all blends exhibit an abrupt increase in conductivity. However, analysis of small-angle X-ray scattering data indicates significant structure even in the disordered state for several blend compositions. By comparing the nature and structure of the disordered states with their corresponding ordered states, we find that this increase in conductivity through the order–disorder transition is most likely due to the elimination of grain boundaries. In either disordered or ordered states, the conductivity decreases as the total amount of homopolymer is increased, an unanticipated observation. This trend with increasing homopolymer loading is hypothesized to result from an increased density of �

Effect of Recycling in Post-Consumer Polystyrene Cups

OpenAIRE

Ahmed, Mehnaz

2016-01-01

The aim of the thesis was to recycle post-consumer polystyrene cups and to analyze the changes in mechanical and rheological properties of the recycled polystyrene. The me-chanical properties were tensile strength, Young’s modulus and the rheological proper-ties was melt flow index. In order to analyze the changes in properties, material testing results of pristine polystyrene were compared with the recycled polystyrene. The same polystyrene material was recycled and tested twice in order to ...

Pearl-necklace complexes of flexible polyanions with neutral-cationic diblock copolymers

NARCIS (Netherlands)

Golinska, M.D.; Wolf, de F.A.; Cohen Stuart, M.A.; Hernandez Garcia, A.; Vries, de R.J.

2013-01-01

We study the complexation of very asymmetric diblock copolymers (consisting of a cationic block of 12 lysines connected to a 400 amino acid long hydrophilic polypeptide block with a net charge that is nearly zero) with oppositely charged sodium poly(acrylic acid) (NaPAA) with a range of molar masses

Evaluation of active sampling strategies for the determination of 1,3-butadiene in air

Science.gov (United States)

Vallecillos, Laura; Maceira, Alba; Marcé, Rosa Maria; Borrull, Francesc

2018-03-01

Two analytical methods for determining levels of 1,3-butadiene in urban and industrial atmospheres were evaluated in this study. Both methods are extensively used for determining the concentration of volatile organic compounds in the atmosphere and involve collecting samples by active adsorptive enrichment on solid sorbents. The first method uses activated charcoal as the sorbent and involves liquid desorption with carbon disulfide. The second involves the use of a multi-sorbent bed with two graphitised carbons and a carbon molecular sieve as the sorbent, with thermal desorption. Special attention was paid to the optimization of the sampling procedure through the study of sample volume, the stability of 1,3-butadiene once inside the sampling tube and the humidity effect. In the end, the thermal desorption method showed better repeatability and limits of detection and quantification for 1,3-butadiene than the liquid desorption method, which makes the thermal desorption method more suitable for analysing air samples from both industrial and urban atmospheres. However, sampling must be performed with a pre-tube filled with a drying agent to prevent the loss of the adsorption capacity of the solid adsorbent caused by water vapour. The thermal desorption method has successfully been applied to determine of 1,3-butadiene inside a 1,3-butadiene production plant and at three locations in the vicinity of the same plant.

Thermal Decomposition of Radiation-Damaged Polystyrene

International Nuclear Information System (INIS)

J Abrefah, J.; Klinger, G.S.

2000-01-01

The radiation-damaged polystyrene material (''polycube'') used in this study was synthesized by mixing a high-density polystyrene (''Dylene Fines No. 100'') with plutonium and uranium oxides. The polycubes were used on the Hanford Site in the 1960s for criticality studies to determine the hydrogen-to-fissile atom ratios for neutron moderation during processing of spent nuclear fuel. Upon completion of the studies, two methods were developed to reclaim the transuranic (TRU) oxides from the polymer matrix: (1) burning the polycubes in air at 873 K; and (2) heating the polycubes in the absence of oxygen and scrubbing the released monomer and other volatile organics using carbon tetrachloride. Neither of these methods was satisfactory in separating the TRU oxides from the polystyrene. Consequently, the remaining polycubes were sent to the Hanford Plutonium Finishing Plant (PFP) for storage. Over time, the high dose of alpha and gamma radiation has resulted in a polystyrene matrix that is highly cross-linked and hydrogen deficient and a stabilization process is being developed in support of Defense Nuclear Facility Safety Board Recommendation 94-1. Baseline processes involve thermal treatment to pyrolyze the polycubes in a furnace to decompose the polystyrene and separate out the TRU oxides. Thermal decomposition products from this degraded polystyrene matrix were characterized by Pacific Northwest National Laboratory to provide information for determining the environmental impact of the process and for optimizing the process parameters. A gas chromatography/mass spectrometry (GC/MS) system coupled to a horizontal tube furnace was used for the characterization studies. The decomposition studies were performed both in air and helium atmospheres at 773 K, the planned processing temperature. The volatile and semi-volatile organic products identified for the radiation-damaged polystyrene were different from those observed for virgin polystyrene. The differences were in the

Flux flow and proximity effects in aligned Pb--Cd eutectic lamellar structures

International Nuclear Information System (INIS)

Spencer, C.R.

1977-09-01

A high speed directional solidification technique was used to fabricate lamellar Pb-Cd and (Pb-Mg)--(Cd-Mg) superconductor-normal metal composites in which all the lamellae are oriented perpendicular to the broad surface of the sample. These lamellar composites are found to behave like a large number (approximately 1000) of superconducting-normal-superconducting junctions. For the Pb-Cd eutectic system, the critical current densities and critical fields have shown no dependence upon the lamellar periods between 1.0 and 3.1 microns. The critical current density of the aligned lamellar Pb-Cd structures was enhanced approximately 50% when compared to quenched eutectic alloy and to pure Pb. The superconducting transition temperature, T/sub c/, varies inversely with the square of the thickness of the superconducting material as expected from Ginzburg-Landau theory. Upon annealing, the Pb lamellae change from type II to type I superconductivity

Flux flow and proximity effects in aligned Pb--Cd eutectic lamellar structures

Energy Technology Data Exchange (ETDEWEB)

Spencer, C. R.

1977-09-01

A high speed directional solidification technique was used to fabricate lamellar Pb-Cd and (Pb-Mg)--(Cd-Mg) superconductor-normal metal composites in which all the lamellae are oriented perpendicular to the broad surface of the sample. These lamellar composites are found to behave like a large number (approximately 1000) of superconducting-normal-superconducting junctions. For the Pb-Cd eutectic system, the critical current densities and critical fields have shown no dependence upon the lamellar periods between 1.0 and 3.1 microns. The critical current density of the aligned lamellar Pb-Cd structures was enhanced approximately 50% when compared to quenched eutectic alloy and to pure Pb. The superconducting transition temperature, T/sub c/, varies inversely with the square of the thickness of the superconducting material as expected from Ginzburg-Landau theory. Upon annealing, the Pb lamellae change from type II to type I superconductivity.

Incorporation of Amphipathic Diblock Copolymer in Lipid Bilayer for Improving pH Responsiveness

Directory of Open Access Journals (Sweden)

Tian Xia

2016-01-01

Full Text Available Diblock copolymers (mPEG-b-PDPA, which were designed to possess pH-sensitivity as well as amphipathy, were used as an intelligent lock in the liposomal membrane. The so-called pH-sensitive liposomes were prepared by simple mixing of the synthesized mPEG-b-PDPA with phospholipids and cholesterol. Fluorescence polarization at pH 7.4 showed that the membrane stability of the hybrid liposome was significantly increased compared with the pure liposome. Therefore, in the neutral environment, the leakage of doxorubicin (DOX was inhibited. However, when pH decreased to 6.0, DOX release rate increased by 60% due to the escape of copolymer. The effects of the membrane composition and the PDPA segment length on bilayer membrane functions were investigated. These results revealed that the synthesized copolymers increased the difference in DOX cumulative release between pH 7.4 and 6.0, that is, improved the pH-controllability of the drug release from hybrid liposomes.

Simple Coatings to Render Polystyrene Protein Resistant

Directory of Open Access Journals (Sweden)

Marcelle Hecker

2018-02-01

Full Text Available Non-specific protein adsorption is detrimental to the performance of many biomedical devices. Polystyrene is a commonly used material in devices and thin films. Simple reliable surface modification of polystyrene to render it protein resistant is desired in particular for device fabrication and orthogonal functionalisation schemes. This report details modifications carried out on a polystyrene surface to prevent protein adsorption. The trialed surfaces included Pluronic F127 and PLL-g-PEG, adsorbed on polystyrene, using a polydopamine-assisted approach. Quartz crystal microbalance with dissipation (QCM-D results showed only short-term anti-fouling success of the polystyrene surface modified with F127, and the subsequent failure of the polydopamine intermediary layer in improving its stability. In stark contrast, QCM-D analysis proved the success of the polydopamine assisted PLL-g-PEG coating in preventing bovine serum albumin adsorption. This modified surface is equally as protein-rejecting after 24 h in buffer, and thus a promising simple coating for long term protein rejection of polystyrene.

Influence of acrylonitrile butadiene rubber on recyclability of blends prepared from poly(vinyl chloride) and poly(methyl methacrylate).

Science.gov (United States)

Suresh, Sunil S; Mohanty, Smita; Nayak, Sanjay K

2018-06-01

The current investigation deals with the recycling possibilities of poly(vinyl chloride) and poly(methyl methacrylate) in the presence of acrylonitrile butadiene rubber. Recycled blends of poly(vinyl chloride)/poly(methyl methacrylate) are successfully formed from the plastic constituents, those are recovered from waste computer products. However, lower impact performance of the blend and lower stability of the poly(vinyl chloride) phase in the recycled blend restricts its further usage in industrial purposes. Therefore, effective utilisation acrylonitrile butadiene rubber in a recycled blend was considered for improving mechanical and thermal performance. Incorporation of acrylonitrile butadiene rubber resulted in the improvement in impact performance as well as elongation-at-break of the recycled blend. The optimum impact performance was found in the blend with 9 wt% acrylonitrile butadiene rubber, which shows 363% of enhancement as compared with its parent blend. Moreover, incorporated acrylonitrile butadiene rubber also stabilises the poly(vinyl chloride) phase present in the recycled blend, similarly Fourier transform infrared spectroscopy studies indicate the interactions of various functionalities present in the recycled blend and acrylonitrile butadiene rubber. In addition to this, thermogravimetric analysis indicates the improvement in the thermal stability of the recycled blend after the addition of acrylonitrile butadiene rubber into it. The existence of partial miscibility in the recycled blend was identified using differential scanning calorimetry and scanning electron microscopy.

Mechanical properties of crossed-lamellar structures in biological shells: A review.

Science.gov (United States)

Li, X W; Ji, H M; Yang, W; Zhang, G P; Chen, D L

2017-10-01

The self-fabrication of materials in nature offers an alternate and powerful solution towards the grand challenge of designing advanced structural materials, where strength and toughness are always mutually exclusive. Crossed-lamellar structures are the most common microstructures in mollusks that are composed of aragonites and a small amount of organic materials. Such a distinctive composite structure has a fracture toughness being much higher than that of pure carbonate mineral. These structures exhibiting complex hierarchical microarchitectures that span several sub-level lamellae from microscale down to nanoscale, can be grouped into two types, i.e., platelet-like and fiber-like crossed-lamellar structures based on the shapes of basic building blocks. It has been demonstrated that these structures have a great potential to strengthen themselves during deformation. The observed underlying toughening mechanisms include microcracking, channel cracking, interlocking, uncracked-ligament bridging, aragonite fiber bridging, crack deflection and zig-zag, etc., which play vital roles in enhancing the fracture resistance of shells with the crossed-lamellar structures. The exploration and utilization of these important toughening mechanisms have attracted keen interests of materials scientists since they pave the way for the development of bio-inspired advanced composite materials for load-bearing structural applications. This article is aimed to review the characteristics of hierarchical structures and the mechanical properties of two kinds of crossed-lamellar structures, and further summarize the latest advances and biomimetic applications based on the unique crossed-lamellar structures. Copyright © 2017 Elsevier Ltd. All rights reserved.

HCP to FCT + precipitate transformations in lamellar gamma-titanium aluminide alloys

Science.gov (United States)

Karadge, Mallikarjun Baburao

Fully lamellar gamma-TiAl [alpha2(HCP) + gamma(FCT)] based alloys are potential structural materials for aerospace engine applications. Lamellar structure stabilization and additional strengthening mechanisms are major issues in the ongoing development of titanium aluminides due to the microstructural instability resulting from decomposition of the strengthening alpha 2 phase. This work addresses characterization of multi-component TiAl systems to identify the mechanism of lamellar structure refinement and assess the effects of light element additions (C and Si) on creep deformation behavior. Transmission electron microscopy studies directly confirmed for the first time that, fine lamellar structure is formed by the nucleation and growth of a large number of basal stacking faults on the 1/6 dislocations cross slipping repeatedly into and out of basal planes. This lamellar structure can be tailored by modifying jog heights through chemistry and thermal processing. alpha 2 → gamma transformation during heating (investigated by differential scanning calorimetry and X-ray diffraction) is a two step process involving the formation of a novel disordered FCC gamma' TiAl [with a(gamma') = c(gamma)] as an intermediate phase followed by ordering. Addition of carbon and silicon induced Ti2AlC H-type carbide precipitation inside the alpha2 lath and Ti 5(Al,Si)3 zeta-type silicide precipitation at the alpha 2/gamma interface. The H-carbides preserve alpha2/gamma type interfaces, while zeta-silicide precipitates restrict ledge growth and interfacial sliding enabling strong resistance to creep deformation.

Bicontinuous Phases in Diblock Copolymer/Homopolymer Blends: Simulation and Self-Consistent Field Theory

KAUST Repository

Martínez-Veracoechea, Francisco J.; Escobedo, Fernando A.

2009-01-01

A combination of particle-based simulations and self-consistent field theory (SCFT) is used to study the stabilization of multiple ordered bicontinuous phases in blends of a diblock copolymer (DBC) and a homopolymer. The double-diamond phase (DD

Effect of shear on cubic phases in gels of a diblock copolymer

DEFF Research Database (Denmark)

Hamley, I.W.; Pople, J.A.; Fairclough, J.P.A.

1998-01-01

The effect of shear on the orientation of cubic micellar phases formed by a poly(oxyethylene)poly(oxybutylene) diblock copolymer in aqueous solution has been investigated using small-angle x-ray scattering (SAXS) and small-angle neutron scattering (SANS). SAXS was performed on samples oriented in...

Hierarchically Ordered Nanopatterns for Spatial Control of Biomolecules

Science.gov (United States)

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

Mechanical behavior and related microstructural aspects of a nano-lamellar TiAl alloy at elevated temperatures

International Nuclear Information System (INIS)

Klein, T.; Usategui, L.; Rashkova, B.; Nó, M.L.; San Juan, J.; Clemens, H.; Mayer, S.

2017-01-01

Advanced intermetallic γ-TiAl based alloys, which solidify via the disordered β phase, such as the TNM"+ alloy, are considered as most promising candidates for structural applications at high temperatures in aero and automotive industries, where they are applied increasingly. Particularly creep resistant microstructures required for high-temperature application, i.e. fine fully lamellar microstructures, can be attained via two-step heat-treatments. Thereby, an increasing creep resistance is observed with decreasing lamellar interface spacing. Once lamellar structures reach nano-scaled dimensions, deformation mechanisms are altered dramatically. Hence, this study deals with a detailed characterization of the elevated temperature deformation phenomena prevailing in nano-lamellar TiAl alloys by the use of tensile creep experiments and mechanical spectroscopy. Upon creep exposure, microstructural changes occur in the lamellar structure, which are analyzed by the comparative utilization of X-ray diffraction, scanning and transmission electron microscopy as well as atom probe tomography. Creep activation parameters determined by mechanical characterization suggest the dominance of dislocation climb by a jog-pair formation process. The dislocations involved in deformation are, in nano-lamellar TiAl alloys, situated at the lamellar interfaces. During creep exposure the precipitation of β_o phase and ζ-silicide particles is observed emanating from the α_2 phase, which is due to the accumulation of Mo and Si at lamellar interfaces.

Disclosed dielectric and electromechanical properties of hydrogenated nitrile–butadiene dielectric elastomer

International Nuclear Information System (INIS)

Yang, Dan; Tian, Ming; Dong, Yingchao; Liu, Haoliang; Yu, Yingchun; Zhang, Liqun

2012-01-01

This paper presents a comprehensive study of the effects of acrylonitrile content, crosslink density and plasticization on the dielectric and electromechanical performances of hydrogenated nitrile–butadiene dielectric elastomer. It was found that by increasing the acrylonitrile content of hydrogenated nitrile–butadiene dielectric elastomer, the dielectric constant will be improved accompanied with a sharp decrease of electrical breakdown strength leading to a small actuated strain. At a fixed electric field, a high crosslink density increased the elastic modulus of dielectric elastomer, but it also enhanced the electrical breakdown strength leading to a high actuated strain. Adding a plasticizer into the dielectric elastomer decreased the dielectric constant and electrical breakdown strength slightly, but reduced the elastic modulus sharply, which was beneficial for obtaining a large strain at low electric field from the dielectric elastomer. The largest actuated strain of 22% at an electric field of 30 kV mm −1 without any prestrain was obtained. Moreover, the hydrogenated nitrile–butadiene dielectric actuator showed good history dependence. This proposed material has great potential to be an excellent dielectric elastomer. (paper)

Fabrication of poly(methyl methacrylate)-block-poly(methacrylic acid) diblock copolymer as a self-embrittling strippable coating for radioactive decontamination

International Nuclear Information System (INIS)

Liu Renlong; Zhang Huiyan; Li Yintao; Zhou Yuanlin; Zhang Quanping; Zheng Jian; Wang Shanqiang

2016-01-01

The poly(methyl methacrylate)-block-poly(methacrylic acid) diblock copolymer with different monomer compositions was synthesized via reversible addition-fragmentation chain transfer polymerization. Meanwhile, a novel self-embrittling strippable coating was prepared using the diblock copolymers, which is proposed to be used as radioactive decontamination agents without manual operation. Furthermore, the decontamination efficiencies of self-embrittling strippable coatings for radioactive contamination on glass, marble, and stainless steel surfaces were studied. (author)

In vitro and in vivo genotoxicity of 1,3-butadiene and metabolites.

OpenAIRE

Arce, G T; Vincent, D R; Cunningham, M J; Choy, W N; Sarrif, A M

1990-01-01

1,3-Butadiene and two major genotoxic metabolites 3,4-epoxybutene (EB) and 1,2:3,4-diepoxybutane (DEB) were used as model compounds to determine if genetic toxicity findings in animal and human cells can aid in extrapolating animal toxicity data to man. Sister chromatid exchange (SCE) and micronucleus induction results indicated 1,3-butadiene was genotoxic in the bone marrow of the mouse but not the rat. This paralleled the chronic bioassays which showed mice to be more susceptible than rats ...

Stability of tetraphenyl butadiene thin films in liquid xenon

International Nuclear Information System (INIS)

Sanguino, P.; Balau, F.; Botelho do Rego, A.M.; Pereira, A.; Chepel, V.

2016-01-01

Tetraphenyl butadiene (TPB) is widely used in particle detectors as a wavelength shifter. In this work we studied the stability of TPB thin films when immersed in liquid xenon (LXe). The thin films were deposited on glass and quartz substrates by thermal evaporation. Morphological and chemical surface properties were monitored before and after immersion into LXe by scanning electron microscopy and X-ray photoelectron spectroscopy. No appreciable changes have been detected with these two methods. Grain size and surface chemical composition were found to be identical before and after submersion into LXe. However, the film thickness, measured via optical transmission in the ultraviolet–visible wavelength regions, decreased by 1.6 μg/cm 2 (24%) after immersion in LXe during 20 h. These results suggest the necessity of using a protective thin film over the Tetraphenyl butadiene when used as a wavelength shifter in LXe particle detectors. - Highlights: • Stability of tetraphenyl butadiene (TPB) thin films immersed in liquid xenon (LXe). • Thermally evaporated TPB thin films were immersed in LXe for 20 h. • Film morphology and chemical surface properties remained unchanged. • Surface density of the films decreased by 1.6 μg/cm 2 (24%) after immersion in LXe. • For using in LXe particle detectors, TPB films should be protected with a coating.

Full color stop bands in hybrid organic/inorganic block copolymer photonic gels by swelling-freezing.

Science.gov (United States)

Kang, Changjoon; Kim, Eunjoo; Baek, Heeyoel; Hwang, Kyosung; Kwak, Dongwoo; Kang, Youngjong; Thomas, Edwin L

2009-06-10

We report a facile way of fabricating hybrid organic/inorganic photonic gels by selective swelling and subsequent infiltration of SiO(2) into one type of lamellar microdomain previously self-assembled from modest-molecular-weight block copolymers. Transparent, in-plane lamellar films were first prepared by assembly of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP), and subsequently the P2VP domains were swollen with a selective solvent, methanol. The swollen structures were then fixated by synthesizing SiO(2) nanoparticles within P2VP domains. The resulting frozen photonic gels (f-photonic gels) exhibited strong reflective colors with stop bands across the visible region of wavelengths.

The Effect of Uncertainty in Exposure Estimation on the Exposure-Response Relation between 1,3-Butadiene and Leukemia

Directory of Open Access Journals (Sweden)

George Maldonado

2009-09-01

Full Text Available Abstract: In a follow-up study of mortality among North American synthetic rubber industry workers, cumulative exposure to 1,3-butadiene was positively associated with leukemia. Problems with historical exposure estimation, however, may have distorted the association. To evaluate the impact of potential inaccuracies in exposure estimation, we conducted uncertainty analyses of the relation between cumulative exposure to butadiene and leukemia. We created the 1,000 sets of butadiene estimates using job-exposure matrices consisting of exposure values that corresponded to randomly selected percentiles of the approximate probability distribution of plant-, work area/job group-, and year specific butadiene ppm. We then analyzed the relation between cumulative exposure to butadiene and leukemia for each of the 1,000 sets of butadiene estimates. In the uncertainty analysis, the point estimate of the RR for the first non zero exposure category (>0–<37.5 ppm-years was most likely to be about 1.5. The rate ratio for the second exposure category (37.5–<184.7 ppm-years was most likely to range from 1.5 to 1.8. The RR for category 3 of exposure (184.7–<425.0 ppm-years was most likely between 2.1 and 3.0. The RR for the highest exposure category (425.0+ ppm-years was likely to be between 2.9 and 3.7. This range off RR point estimates can best be interpreted as a probability distribution that describes our uncertainty in RR point estimates due to uncertainty in exposure estimation. After considering the complete probability distributions of butadiene exposure estimates, the exposure-response association of butadiene and leukemia was maintained. This exercise was a unique example of how uncertainty analyses can be used to investigate and support an observed measure of effect when occupational exposure estimates are employed in the absence of direct exposure measurements.

Studies on microphase-separated structures of block copolymers by neutron reflectivity measurement

International Nuclear Information System (INIS)

Torikai, Naoya; Noda, Ichiro; Matsushita, Yushu; Karim, A.; Satija, S.K.; Han, C.C.; Ebisawa, Toru.

1996-01-01

Segmental distributions of block copolymer chains in lamellar microphase-separated structure and those of homopolymers in block copolymer/homopolymer blends also with lamellar structures were studied by neutron reflectivity measurements. It was revealed that polystyrene and poly(2-vinylpyridine) lamellae were alternately stacked within the thin films of pure block copolymers spin-coated on silicon wafers, and they were preferentially oriented along the direction parallel to film surface. Polystyrene lamella appeared at air surfaces of the films, while poly(2-vinylpyridine) lamella did on silicon surfaces. Segment distribution at lamellar interface was well described by an error function, and the width of the lamellar interface, defined by a full-width half-maximum value of interfacial profile, was estimated to be about 4.5 nm. Segments of block chains adjacent to the chemical junction points connecting different block chains were strongly localized near the lamellar interfaces, while those on the free ends of block chains were distributed all over the lamellar microdomains with their distribution maxima at the centers of lamellae. On the other hand, it was clarified that homopolymers dissolved in the corresponding lamellar microdomains of block copolymers were also distributed throughout the microdomains with their concentration maxima at the centers of the lamellae. (author)

Mechanical properties of a waterborne pressure-sensitive adhesive with a percolating poly(acrylic acid)-based diblock copolymer network: effect of pH.

Science.gov (United States)

Gurney, Robert S; Morse, Andrew; Siband, Elodie; Dupin, Damien; Armes, Steven P; Keddie, Joseph L

2015-06-15

Copolymerizing an acrylic acid comonomer is often beneficial for the adhesive properties of waterborne pressure-sensitive adhesives (PSAs). Here, we demonstrate a new strategy in which poly(acrylic acid) (PAA) is distributed as a percolating network within a PSA film formed from a polymer colloid. A diblock copolymer composed of PAA and poly(n-butyl acrylate) (PBA) blocks was synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization and adsorbed onto soft acrylic latex particles prior to their film formation. The thin adsorbed shells on the particles create a percolating network that raises the elastic modulus, creep resistance and tensile strength of the final film. When the film formation occurs at pH 10, ionomeric crosslinking occurs, and high tack adhesion is obtained in combination with high creep resistance. The results show that the addition of an amphiphilic PAA-b-PBA diblock copolymer (2.0 wt.%) to a soft latex provides a simple yet effective means of adjusting the mechanical and adhesive properties of the resulting composite film. Copyright © 2015 Elsevier Inc. All rights reserved.

Polystyrene/Hyperbranched Polyester Blends and Reactive Polystyrene/Hyperbranched Polyester Blends

National Research Council Canada - National Science Library

Mulkern, Thomas

1999-01-01

.... In this work, the incorporation of HBPs in thermoplastic blends was investigated. Several volume fractions of hydroxyl functionalized hyperbranched polyesters were melt blended with nonreactive polystyrene (PS...

Surfactant assisted synthesis of lamellar nanostructured LiFePO4 at 388 K

International Nuclear Information System (INIS)

Liu Chao; Ma Dongxia; Ji Xiujie; Zhao Shanshan; Li Song

2011-01-01

Lamellar nanostructured lithium iron phosphate (Lα-LFP) was synthesized using anion surfactant sodium dodecyl sulphonate (SDS) as supermolecular template in water-ethanol media at 388 K under self-generated pressure. FeSO 4 , (NH 4 ) 2 HPO 4 and LiOH were used as Fe, P and Li sources, respectively. The inorganic phase was analyzed by X-ray diffraction (XRD). The morphology and the lamellar nanostructure were observed by field emitting scanning electron microscopy (FESEM). The results showed that the synthesized Lα-LFP presents not only the ordered lamellar microstructure accumulated by 20-40-nm thick LFP layers, but also the consequent self-assembled blocky particles of 0.5-1 μm. In contrast, template free LFP (TF-LFP) show a flake-shaped and mess-orientated microstructure. As a soft template, SDS played the roles of inducing the lamellar nanostructure, purifying the inorganic phase and decreasing the synthesis temperature.

''Nonisolated-sensor'' solid polystyrene absorbed dose measurements

International Nuclear Information System (INIS)

Zeitz, L.; Laughlin, J.S.

1982-01-01

A ''nonisolated-sensor'' solid polystyrene calorimeter was constructed to test the role of thermal diffusion in limiting the length of irradiation time during which temperature measurements with nonisolated sensors could be made sufficiently free of drift for determining dose with radiation fields such as gamma rays, x rays, and high-energy electrons. From measured ratios of dose at 5.0 and 0.5 cm in polystyrene and comparisons to dose measurements with a polystyrene parallel-plate (pancake) ion chamber, it was shown that thermal diffusion is sufficiently small in polystyrene to permit accurate measurements for irradiation periods of less than 20 min. Comparison of the absorbed dose measurements and depth dose ratios with pancake ion chambers and calorimeter showed, that within the precision and accuracy of the two measuring systems, there is close agreement. The nonisolated-sensor solid polystyrene calorimeter has the interesting features of (i) simplicity of construction, (ii) simplicity of operation without vacuum or feedback for temperature control, (iii) capability of simultaneous measurements at several depths and off-axis positions, (iv) the very small thermal defect correction with polystyrene, and (v) operation with the calorimeter in any orientation

Nonisolated-sensor solid polystyrene absorbed dose measurements

International Nuclear Information System (INIS)

Zeitz, L.; Laughlin, J.S.

1982-01-01

A nonisolated-sensor solid polystyrene calorimeter was constructed to test the role of thermal diffusion in limiting the length of irradiation time during which temperature measurements with nonisolated sensors could be made sufficiently free of drift for determining dose with radiation fields such as gamma rays, x rays, and high-energy electrons. From measured ratios of dose at 5.0 and 0.5 cm in polystyrene and comparisons to dose measurements with a polystyrene parallel-plate (pancake) ion chamber, it was shown that thermal diffusion is sufficiently small in polystyrene to permit accurate measurements for irradiation periods of less than 20 min. Comparison of the absorbed dose measurements and depth dose ratios with pancake ion chambers and calorimeter showed, that within the precision and accuracy of the two measuring systems, there is close agreement. The nonisolated-sensor solid polystyrene calorimeter has the interesting features of (i) simplicity of construction, (ii) simplicity of operation without vacuum or feedback for temperature control, (iii) capability of simultaneous measurements at several depths and off-axis positions, (iv) the very small thermal defect correction with polystyrene, and (v) operation with the calorimeter in any orientation

State of mixing of deuterated and non-deuterated block polymer chains

International Nuclear Information System (INIS)

Hasegawa, Hirokazu; Hashimoto, Takeji

1984-01-01

Prior to the small-angle neutron scattering study on the conformation of block polymer chains in the domain space, the state of mixing of two block polymers, an ordinary polystyrene-polyisoprene diblock polymer and a poly(deuterated styrene)-polyisoprene diblock polymer with a different molecular weight and composition, was investigated by a small-angle X-ray scattering (SAXS) technique. Only one kind of domain structure was observed for each blend, and the domain spacings obtained by SAXS were proportional to the two-thirds power of the number-average molecular weight of the blends (reduced to non-deuterated block polymer). The volume fractions of polystyrene domain in the blends evaluated by computer simulation of SAXS profiles well agreed with the values estimated from blend composition. All these facts suggest the molecular mixing of the two block polymers in the domain space. (author)

An ingenious design of lamellar Li1.2Mn0.54Ni0.13Co0.13O2 hollow nanosphere cathode for advanced lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Yao; Zhang, Wansen; Shen, Shuiyun; Yan, Xiaohui; Wu, Aiming; Wu, Ruofei; Zhang, Junliang

2017-01-01

Highlights: •Lamellar Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 hollow nanospheres serve as a cathode for LIBs. •Unique lamella and hollow structures benefit the enhanced electrochemical performance. •Lamellar shells can provide a short lithium-ion diffusion pathway. •The sufficient void space can accommodate volumetric expansion and contraction. -- Abstract: Although very appealing in developing hollow structured lithium-rich layered transition-metal oxides as cathodes for lithium-ion batteries (LIBs), a great challenge lies in controlling the growth of transition metal elements with desired molar ratios while maintaining intact hollow structures during synthesis. Herein, we propose a scalable strategy to successfully synthesize novel lamellar Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 hollow (L-LMOH) nanosphere cathode for advanced lithium-ion batteries (LIBs). It is proved that the employment of sulfonated polystyrene (SPS) gel nanospheres as the template plays a key role in the formation of flower-like SPS@ Ni-Co-Mn-precursor nanospheres with desired molar ratios, and a subsequently delicate control in the heating rate leads to the intact L-LMOH nanospheres. It is demonstrated that the use of L-LMOH nanosphere cathode not only delivers outstanding reversible discharge capacities of 281.7 mAh g −1 at a current density of 20 mA g −1 and 136.6 mAh g −1 at 2000 mA g −1 , but also possess superior cycling stability with a capacity reservation of 80% at 2000 mA g −1 after 200 continuous cycles. It is well analyzed that the ingenious design of both unique lamella and hollow architectures synergistically benefits the significantly enhanced rate capability and cycling stability.

Synthesis, characterization and photoinduction of optical anisotropy in liquid crystalline diblock azo-copolymers

NARCIS (Netherlands)

Forcen, P.; Oriol, L.; Sanchez, S.; Alcala, R.; Hvilsted, S.; Jankova, K.; Loos, J.

2007-01-01

Diblock copolymers with polymethyl methacrylate and side chain liquid crystalline (LC) azopolymethacrylate blocks were synthesized by atom transfer radical polymerization (ATRP). The azobenzene content in these copolymers ranges from 52 to 7 wt %. For an azo content down to 20% they exhibit a LC

Adsorption kinetics of diblock copolymers from a micellar solution on silica and titania.

NARCIS (Netherlands)

Bijsterbosch, H.D.; Cohen Stuart, M.A.; Fleer, G.J.

1998-01-01

The solution and adsorption behavior of a series of diblock copolymers of hydrophobic poly(dimethyl siloxane) and hydrophilic poly(2-ethyl-2-oxazoline) was studied. These block copolymers formed large polydisperse micelles in an aqueous solution. The critical micelle concentration was lower than 2

Highly-Ordered Magnetic Nanostructures on Self-Assembled α-Al2O3 and Diblock Copolymer Templates

International Nuclear Information System (INIS)

Erb, Denise

2015-08-01

This thesis shows the preparation of nanostructured systems with a high degree of morphological uniformity and regularity employing exclusively selfassembly processes, and documents the investigation of these systems by means of atomic force microscopy (AFM), grazing incidence small angle X-ray scattering (GISAXS), and nuclear resonant scattering of synchrotron radiation (NRS). Whenever possible, the X-ray scattering methods are applied in-situ and simultaneously in order to monitor and correlate the evolution of structural and magnetic properties of the nanostructured systems. The following systems are discussed, where highly-ordered magnetic nanostructures are grown on α-Al 2 O 3 substrates with topographical surface patterning and on diblock copolymer templates with chemical surface patterning: - Nanofaceted surfaces of α-Al 2 O 3 - Magnetic nanostructures on nanofaceted α-Al 2 O 3 substrates - Thin films of microphase separated diblock copolymers - Magnetic nanostructures on diblock copolymer thin film templates The fact that the underlying self-assembly processes can be steered by external factors is utilized to optimize the degree of structural order in the nanostructured systems. The highly-ordered systems are well-suited for investigations with X-ray scattering methods, since due to their uniformity the inherently averaged scattered signal of a sample yields meaningful information on the properties of the contained nanostructures: By means of an in-situ GISAXS experiment at temperatures above 1000 C, details on the facet formation on α-Al 2 O 3 surfaces are determined. A novel method, merging in-situ GISAXS and NRS, shows the evolution of magnetic states in a system with correlated structural and magnetic inhomogeneity with lateral resolution. The temperature-dependence of the shape of Fe nanodots growing on diblock copolymer templates is revealed by in-situ GISAXS during sputter deposition of Fe. Combining in-situ GISAXS and NRS, the magnetization

Radiation-induced polymerization of 1, 3-butadiene in urea canal complex as studied by broad line NMR

International Nuclear Information System (INIS)

Yoshii, Fumio; Hayakawa, Naohiro; Abe, Toshihiko

1975-01-01

Dependence of the NMR spectrum on the molar ratio of 1,3-butadiene to urea, temperature dependence of the spectrum and changes of the spectrum during polymerization were observed. The results were discussed in comparison with previously reported results for the canal polymerization of acrylonitrile and vinyl chloride. 1,3-butadiene formes a canal complex with the molar ratio of 1 to 4 for 1,3-butadiene to urea. The urea canal complex is decomposed at -15 0 C. The spectrum of 1,3-butadiene in urea canal complex shows existence of a remarkably mobile component which was not observed on the spectra of acrylonitrile - urea of vinyl chloride - urea canal complex. The line width of 1,3-butadiene in the urea canal complex except the very narrow component was broader than that for vinyl chloride in the urea canal complex over an observed temperature range. The line width of urea formed the canal decreases at lower temperature than those of urea in vinyl chloride - urea canal complex. The post-polymerization of 1,3-butadiene in the urea canal complex started clearly from -78 0 C and completes when the temperature was raised to 20 0 C. The polymerization will be proceeded by the such way that monomer molecules move to the active center in the canal, as considered in the case of the polymerization of acrylonitrile and vinyl chloride in the canal complex. The crystal structure of the urea canal was maintained during polymerization and than the polybutadiene - urea canal complex was necessarily formed after the polymerization. The formation of the polymer - urea canal complex has distinct difference between 1,3-butadiene and acrylonitrile or vinyl chloride. For acrylonitrile and vinyl chloride the canals around the polymer formed are destroyed. The structure of polybutadiene - urea canal complex was hexagonal having a=8.21, c=10.50 A. (auth.)

Effects of PEO-PPO diblock impurities on the cubic structure of aqueous PEO-PPO-PEO pluronics micelles: fcc and bcc ordered structures in F127

DEFF Research Database (Denmark)

Mortensen, Kell; Pedersen, Walther Batsberg; Hvidt, S.

2008-01-01

We report on structural properties of PEO-PPO-PEO type of triblock block copolymers (Pluronics F127) with special emphasis on the effect of diblock PEO-PPO impurities on the ordered gel phase. Commercial F127 polymers contain as received roughly 20% PEO-PPO diblock and 80% PEO-PPO-PEO triblock...... copolymers. Aqueous solutions of F127 copolymers used as received form fee ordered micellar structure. Copolymers depleted with respect to the diblock impurity, resulting in a pure PEO-PPO-PEO triblock copolymer system, form bcc ordered micelles within the major parts of the gel phase. However, close...

Self-assembled block copolymer photonic crystal for selective fructose detection.

Science.gov (United States)

Ayyub, Omar B; Ibrahim, Michael B; Briber, Robert M; Kofinas, Peter

2013-08-15

The use of one-dimensional photonic crystals fabricated from a self-assembled lamellar block copolymer as a sensitive and selective fructose sensor is investigated. The polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) films are functionalized with 2-(bromomethyl)phenylboronic acid. The boronic acid moiety confined within the lamellar morphology can reversibly bind to sugars such as fructose, imparting the photonic properties of the PS-b-P2VP film. The films exhibit a detection limit of 500 μM in water and 1mM in phosphate buffered saline. Exposure to a 50 mM solution of fructose invokes a highly visible color change from blue to orange. The films are also able to selectively recognize and respond to fructose in competitive studies in the presence of glucose, mannose and sucrose. Copyright © 2013 Elsevier B.V. All rights reserved.

Biocompatibility of epoxidized styrene-butadiene-styrene block copolymer membrane

International Nuclear Information System (INIS)

Yang, Jen Ming; Tsai, Shih Chang

2010-01-01

Styrene-butadiene-styrene block copolymer (SBS) membrane was prepared by solution casting method and then was epoxidized with peroxyformic acid generated in situ to yield the epoxidized styrene-butadiene-styrene block copolymer membrane (ESBS). The structure and properties of ESBS were characterized with infrared spectroscopy, Universal Testing Machine, differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). The performances of contact angle, water content, protein adsorption, and water vapor transmission rate on ESBS membrane were determined. After epoxidation, the hydrophilicity of the membrane increased. The water vapor transmission rate of ESBS membrane is similar to human skin. The biocompatibility of ESBS membrane was evaluated with the cell culture of fibroblasts on the membrane. It revealed that the cells not only remained viable but also proliferated on the surface of the various ESBS membranes and the population doubling time for fibroblast culture decreased.

Environmentally benign electroless nickel plating using supercritical carbon-dioxide on hydrophilically modified acrylonitrile-butadiene-styrene

Science.gov (United States)

Tengsuwan, Siwach; Ohshima, Masahiro

2014-08-01

Electroless Ni-P plating using supercritical carbon dioxide (scCO2) in conjunction with copolymer-based hydrophilic modification was applied to an acrylonitrile-butadiene-styrene (ABS) substrate. The surface of ABS substrate was hydrophilically modified by blending with a multi-block copolymer, poly(ether-ester-amide)s (PEEA), in injection molding process. The substrate was then impregnated with Pd(II)-hexafluoroacetylacetonate, Pd(hfa)2, using scCO2, followed by the electroless plating reaction. ABS/PEEA substrates with different PEEA to ABS blend ratios and different volume ratios of butadiene to the styrene-acrylonitrile copolymer (SAN) matrix were prepared to investigate how the dispersed PEEA and butadiene domains affected the blend morphology and the adhesive strength of the plating metal-to-polymer contact. Increasing the PEEA copolymer to ABS blend ratio increased the mass transfer rate of the plating solution in the ABS substrate. Consequently, the metal-polymer composite layer became thicker, which increased the adhesive strength of the metal-to-polymer contact because of the anchoring effect. The butadiene domains appeared to attract the Pd catalyst precursor, and thus, the proportion of butadiene in the ABS matrix also affected the adhesive strength of the contact between the metal layer and the substrate. The ABS substrate was successfully plated with a Ni-P metal layer with an average adhesive strength of 9.1 ± 0.5 N cm-1 by choosing appropriate ABS/PEEA blend ratios and a Pd(hfa)2 concentration.

Effect of reactive monomer on PS-b-P2VP film with UV irradiation

Science.gov (United States)

Kim, H. J.; Shin, D. M.

2012-03-01

Poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) lamellar film which is hydrophobic block hydrophilic polyelectrolyte block polymer of 52 kg/mol -b- 57 kg/mol and PS-b-P2VP film with reactive monomer (RM257) were prepared for photonic gel films. The lamellar stacks, which is alternating layer of hydrophilic and hydrophobic part of PS-b-P2VP. We reported about the influence of reactive monomer on those photonic gel films. Added reactive monomer photonic gel film had higher absorbance than pure photonic gel films. And band gaps of the lamellar films shifted by the time of UV light irradiation. That Photonic gel films were measured with the UV spectrophotometer. As a result the photonic gel film with reactive monomer had more clear color. The lamellar films were swollen by DI water, Ethyl alcohol (aq) and calcium carbonate solution. Since the domain spacing of dried photonic gel films were not showing any color in visible wavelength. The band gap of the lamellar films were drastically shifted to longer wavelength swollen by calcium carbonate solution (absorbance peak 565nm-->617nm). And the lamellar films were shifted to shorter wave length swollen by ethanol (absorbance peak 565nm-->497nm). So each Photonic gel film showed different color.

Analysis of Lamellar Structures with Application of Generalized Functions

Directory of Open Access Journals (Sweden)

Kipiani Gela

2016-12-01

Full Text Available Theory of differential equations in respect of the functional area is based on the basic concepts on generalized functions and splines. There are some basic concepts related to the theory of generalized functions and their properties are considered in relation to the rod systems and lamellar structures. The application of generalized functions gives the possibility to effectively calculate step-variable stiffness lamellar structures. There are also widely applied structures, in that several in which a number of parallel load bearing layers are interconnected by discrete-elastic links. For analysis of system under study, such as design diagrams, there are applied discrete and discrete-continual models.

Magnetic properties of lamellar tetrataenite in Toluca iron meteorite

International Nuclear Information System (INIS)

Funaki, Minoru; Nagata, Takesi; Danon, J.

1985-01-01

Magnetic studies were conducted using lamellar tetrataenite extracted from the Toluca octahedrite by a diluted HCl etching technique. Natural remanent magnetization (NRM) in the lamellae is very stable against AF demagnetization and is quite intense, ranging from 2.58 to 37.42 x10 -2 emu/g. This NRM is completely demagnetized thermally at about 550 0 C. The most characteristic change in magnetic properties on heating to about 550 C 0 is a significant decrease in magnetic coercivity. This observation is consistent with the results obtained from chondrites. The paramagnetic component in lamellar tetrataenite, which is estimated by Moessbauer spectrum analyses, was not detected by conventional magnetic studies. (Author) [pt

Strengthening behavior of beta phase in lamellar microstructure of TiAl alloys

Science.gov (United States)

Zhu, Hanliang; Seo, D. Y.; Maruyama, K.

2010-01-01

β phase can be introduced to TiAl alloys by the additions of β stabilizing elements such as Cr, Nb, W, and Mo. The β phase has a body-centered cubic lattice structure and is softer than the α2 and γ phases in TiAl alloys at elevated temperatures, and hence is thought to have a detrimental effect on creep strength. However, fine β precipitates can be formed at lamellar interfaces by proper heat treatment conditions and the β interfacial precipitate improves the creep resistance of fully lamellar TiAl alloys, since the phase interface of γ/β retards the motion of dislocations during creep. This paper reviews recent research on high-temperature strengthening behavior of the β phase in fully lamellar TiAl alloys.

Quantitative analysis of lamellar bodies in amniotic fluid as fetal pulmonary maturity indicator

Directory of Open Access Journals (Sweden)

Ljubić Vesna

2009-01-01

Full Text Available Background/Aim. Although lamellar bodies have been the center of interest over the last years, the published results of fetal pulmonary maturity determination according to their concentration in amniotic fluid are controversial. The aim of this study was to determine the significance of lamellar bodies, as well as the ratio lecithin/sphingomyelin (L/S in amniotic fluid for the assessment of fetal pulmonary maturity. Methods. This prospective 2-year study included 102 female examinees, ranging from 17 to 44 years of age, in whom lamellar bodies concentrations in amniotic fluid were determined to check the efficacy of the applied therapy for obtaining arteficial fetal pulmonary maturity. The shake test was applied as a comparative test for determining a quantitative L/S ratio. To determine a fetus maturity and development stage we followed up biparietal diameter, abdominal circumference, femure length, ponderal index at birth and body mass. Results. Out of a total of 102 amniocenteses within a period from 26th to 40th gestation week only 70 results were considered due to 32 unknown neonatal outcomes. Biparietal diameter was 224-362 mm, femur length 56 - 78 mm, ponderal index 1.22-2.84, fetus body mass 1300- 4 350 g. There was found a significant relation between gestation age and lamellar bodies concentration (R = 0.396398, p < 0.01, as well as between gestation age and the ratio L/S (R = 0.691297, p < 0.01. Also, there was a significant correlation of lamellar bodies concentration to the ratio L/S determined (R = 0.493609, p < 0.01. Conclusion. Determination of lamellar bodies concentration values is a reliable method to confirm fetal pulmonary maturity.

Advanced analytical methods for the structure elucidation of polystyrene-b-poly(n-butyl acrylate) block copolymers prepared by reverse iodine transfer polymerisation

Energy Technology Data Exchange (ETDEWEB)

Wright, Trevor Gavin; Pfukwa, Helen; Pasch, Harald, E-mail: hpasch@sun.ac.za

2015-09-10

Reverse iodine transfer polymerisation (RITP) is a living radical polymerisation technique that has shown to be feasible in synthesising segmented styrene-acrylate copolymers. Polymers synthesised via RITP are typically only described regarding their bulk properties using nuclear magnetic resonance spectroscopy and size exclusion chromatography. To fully understand the complex composition of the polymerisation products and the RITP reaction mechanism, however, it is necessary to use a combination of advanced analytical methods. In the present RITP procedure, polystyrene was synthesised first and then used as a macroinitiator to synthesise polystyrene-block-poly(n-butyl acrylate) (PS-b-PBA) block copolymers. For the first time, these PS-b-PBA block copolymers were analysed by a combination of SEC, in situ{sup 1}H NMR and HPLC. {sup 1}H NMR was used to determine the copolymer composition and the end group functionality of the samples, while SEC and HPLC were used to confirm the formation of block copolymers. Detailed information on the living character of the RITP process was obtained. - Highlights: • Comprehensive analysis of novel block copolymers. • Polymers were prepared for the first time by reverse iodine transfer polymerisation. • Combination of SEC, NMR, kinetic NMR, HPLC and comprehensive 2D-HPLC was used. • Detailed information about complex molecular composition and polymerisation kinetics was obtained.

A molecular dynamics study on Young's modulus and tribology of carbon nanotube reinforced styrene-butadiene rubber.

Science.gov (United States)

Chawla, Raj; Sharma, Sumit

2018-03-18

Styrene-butadiene rubber is a copolymer widely used in making car tires and has excellent abrasion resistance. The Young's modulus and tribology of pure styrene butadiene rubber (SBR) polymer and carbon nanotube reinforced polymer composites have been investigated using molecular dynamics simulations. The mechanism of enhanced tribology properties using carbon nanotube has been studied and discussed. The obtained Young's modulus shows the enhancement in mechanical properties of SBR polymer when carbon nanotubes are used as reinforcement. The concentration, temperature and velocity profiles, radial distribution function, frictional stresses, and cohesive energy density are calculated and analyzed in detail. The Young's modulus of SBR matrix increases about 29.16% in the presence of the 5% CNT. The atom movement velocity and average cohesive energy density in the friction area of pure SBR matrix was found to be more than that of the CNT/SBR composite. Graphical abstract Initial and final conditions of (a) pure SBR matrix and (b) CNT/SBR matrix subjected toshear loading and frictional stresses of top Fe layers of both pure SBR and CNT/SBR composite.

High-density arrays of titania nanoparticles using monolayer micellar films of diblock copolymers as templates.

Science.gov (United States)

Li, Xue; Lau, King Hang Aaron; Kim, Dong Ha; Knoll, Wolfgang

2005-05-24

Highly dense arrays of titania nanoparticles were fabricated using surface micellar films of poly(styrene-block-2-vinylpyridine) diblock copolymers (PS-b-P2VP) as reaction scaffolds. Titania could be introduced selectively within P2VP nanodomains in PS-b-P2VP films through the binary reaction between water molecules trapped in the P2VP domains and the TiCl(4) vapor precursors. Subsequent UV exposure or oxygen plasma treatment removed the organic matrix, leading to titania nanoparticle arrays on the substrate surface. The diameter of the titania domains and the interparticle distance were defined by the lateral scale present in the microphase-separated morphology of the initial PS-b-P2VP films. The typical diameter of titania nanoparticles obtained by oxygen plasma treatment was of the order of approximately 23 nm. Photoluminescence (PL) properties were investigated for films before and after plasma treatment. Both samples showed PL properties with major physical origin due to self-trapped excitons, indicating that the local environment of the titanium atoms is similar.

Development of lamellar structures in natural waxes - an electron diffraction investigation

Science.gov (United States)

Dorset, Douglas L.

1999-06-01

When they are recrystallized from the melt, natural plant or insect waxes tend to form solid phases with a nematic-like structure (i.e. a parallel array of polymethylene chains with little or no aggregation of the molecules into distinct layers). An electron diffraction study of carnauba wax and two types of beeswax has shown that the degree of molecular organization into lamellar structures can be enhanced by annealing in the presence of benzoic acid, which also acts as an epitaxial substrate. Nevertheless, the resultant layer structure in the annealed solid is not the same as that found for paraffin wax fractions refined from petroleum. Probably because of a small but significant fraction of a very long chain ingredient, the lamellar separation is incomplete, incorporating a number of `bridging molecules' that span the nascent lamellar interface.The same phenomenon has been described recently for a low molecular weight polyethylene.

Promoting effect of oxygen for hydrogenation of butadiene over Ni/sub 2/P catalyst

Energy Technology Data Exchange (ETDEWEB)

Nozaki, F.; Kitoh, T.; Sodesawa, T.

1980-04-01

When 0-10 mm Hg of oxygen were added to the reaction of 75 mm Hg butadiene and 225 mm Hg hydrogen over dinickel phosphide in a closed circulation system at 40/sup 0/C, increasing amounts of oxygen caused increasing lengths of induction periods followed by hydrogenation at reaction rates which had a maximum at 3 mm Hg oxygen. This maximum rate was about six times higher than the rate without oxygen addition. Adsorption, temperature-programed desorption, IR spectroscopy, and the product distribution of butadiene deuteration showed that two types of oxygen adsorbed on the dinickel phosphide catalyst; molecular oxygen on nickel, which desorbed on evacuation below 50/sup 0/C and which could be displaced by butadiene, was responsible for the induction period; molecular oxygen on phosphorus atoms, which promoted hydrogen adsorption, was responsible for the increased hydrogenation rate.

Influence of SEBS-MA and SBS compatibilizers on properties and morphology of blends of polystyrene/rubber residue (SBRr from the footwear industry

Directory of Open Access Journals (Sweden)

Carlos Bruno Barreto Luna

Full Text Available Abstract The reuse of rubber waste is very important today, both to reduce the harmful effects on the environment, and to reduce the cost of new material development. Considering that most of the studies reported in literature refer to the reuse of tire waste, this article aims to evaluate the influence of styrene-butadiene-styrene (SBS and styrene-(ethylene-butylene-styrene grafted with maleic anhydride (SEBS-MA compatibilizers on the blend performance of polystyrene (PS/styrene-butadiene rubber residue (SBRr, which come from the footwear industry. The blends were prepared in a co-rotating twin screw extruder and then were molded by injection. They were analyzed by impact and tensile tests, heat deflection temperature (HDT, ductile-brittle transition temperature, dynamic mechanical thermal analysis (DMTA and transmission electron microscopy (TEM. The results evidenced that the use of any of the compatibilizers on the PS/SBRr blend significantly increased the impact strength, while the tensile properties and HDT were lower when compared to the polymer matrix. The ductile-brittle transition temperature remains at approximately 25°C range for all the blends. In general, it has been proved that the SBS was the most effective compatibilization process in the PS/SBRr system. The DMTA test shows the presence of two distinct temperature peaks. The morphologies obtained by TEM of binary and ternary blends were quite different and typical of immiscible blend. The results show a good perspective regarding the use of industrial waste (SBRr, since it may enhance a material that would be discarded.

Modeling creep deformation of a two-phase TiAI/Ti3Al alloy with a lamellar microstructure

Science.gov (United States)

Bartholomeusz, Michael F.; Wert, John A.

1994-10-01

A two-phase TiAl/Ti3Al alloy with a lamellar microstructure has been previously shown to exhibit a lower minimum creep rate than the minimum creep rates of the constituent TiAl and Ti3Al single-phase alloys. Fiducial-line experiments described in the present article demonstrate that the creep rates of the constituent phases within the two-phase TiAl/Ti3Al lamellar alloy tested in compression are more than an order of magnitude lower than the creep rates of single-phase TiAl and Ti3Al alloys tested in compression at the same stress and temperature. Additionally, the fiducial-line experiments show that no interfacial sliding of the phases in the TiAl/Ti3Al lamellar alloy occurs during creep. The lower creep rate of the lamellar alloy is attributed to enhanced hardening of the constituent phases within the lamellar microstructure. A composite-strength model has been formulated to predict the creep rate of the lamellar alloy, taking into account the lower creep rates of the constituent phases within the lamellar micro-structure. Application of the model yields a very good correlation between predicted and experimentally observed minimum creep rates over moderate stress and temperature ranges.

1,3-Butadiene: Biomarkers and application to risk assessment

Czech Academy of Sciences Publication Activity Database

Swenberg, J. A.; Bordeerat, N. K.; Boysen, G.; Carro, S.; Georgieva, N. I.; Troutman, J. M.; Upton, P. B.; Albertini, R. J.; Vacek, P. M.; Walker, V. E.; Šrám, Radim; Goggin, M.; Tretyakova, N.

2011-01-01

Roč. 192, 1-2 (2011), s. 150-154 ISSN 0009-2797 Institutional research plan: CEZ:AV0Z50390512 Keywords : risk assessment * 1,3-butadiene * occupational exposure Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 2.865, year: 2011

Lamellar ichthyosis (collodian baby with severe bilateral ectropion

Directory of Open Access Journals (Sweden)

Boparai M

1988-01-01

Full Text Available A case of lamellar ichthyosis (collodian baby, is being reported. Skin biopsy has confirmed the diagnosis. Severe bilateral ectropion of thee eyelids was the prominent feature. Management of such cases has been briefly discussed.

Micro alloyed steel weldability and sensibility testing on the lamellar cracks appearance

Directory of Open Access Journals (Sweden)

S. Stojadinović

2011-07-01

Full Text Available In this work are given the testing results of mechanical properties welded joints and microstructure of micro alloyed steel as well as its sensitivity to lamellar cracks appearance. The obtained results show that steel has good resistance to lamellar cracks appearance and with an appropriate wire choice for welding, a good combination of mechanical properties could be obtained at room (ambience temperatures as well as at low temperatures.

Development of lamellar structures in natural waxes - an electron diffraction investigation

Energy Technology Data Exchange (ETDEWEB)

Dorset, Douglas L. [Electron Diffraction Department, Hauptman-Woodward Medical Research Institute, Inc., Buffalo, NY (United States)

1999-06-07

When they are recrystallized from the melt, natural plant or insect waxes tend to form solid phases with a nematic-like structure (i.e. a parallel array of polymethylene chains with little or no aggregation of the molecules into distinct layers). An electron diffraction study of carnauba wax and two types of beeswax has shown that the degree of molecular organization into lamellar structures can be enhanced by annealing in the presence of benzoic acid, which also acts as an epitaxial substrate. Nevertheless, the resultant layer structure in the annealed solid is not the same as that found for paraffin wax fractions refined from petroleum. Probably because of a small but significant fraction of a very long chain ingredient, the lamellar separation is incomplete, incorporating a number of 'bridging molecules' that span the nascent lamellar interface.The same phenomenon has been described recently for a low molecular weight polyethylene. (author)

A structural study of lamellar phases formed by nucleoside-functionalized lipids

CERN Document Server

Berti, D; Baglioni, P; Dante, S; Hauss, T

2002-01-01

We report a neutron-scattering investigation of lamellar phases formed by novel phospholipids bearing nucleosides at the polar-head-group region. These nucleolipids can interact through stacking and H-bond interactions, following a pattern that resembles base-base coupling in natural nucleic acids (DNA, RNA), i.e. they have similar recognition properties. Bilayer stacks formed of DPP-adenosine, DPP-uridine and their 1:1 mixture were investigated after equilibration in a 98% relative humidity atmosphere. The DPP-adenosine spectrum can be accounted for (in analogy to DPPC) by a lamellar phase with a smectic period of about 60 A. DPP-uridine displays a not so straightforward behavior that we have tentatively ascribed to the coexistence of lamellae with different smectic periods. In the 1:1 mixture the lamellar mesophase of DPP-uridine is retained, suggesting a specific interaction of the uridine polar-head group with the adenosine moiety of DPP-adenosine. It should be stressed that this behavior can be considere...

Hydrogen bonding strength of diblock copolymers affects the self-assembled structures with octa-functionalized phenol POSS nanoparticles.

Science.gov (United States)

Lu, Yi-Syuan; Yu, Chia-Yu; Lin, Yung-Chih; Kuo, Shiao-Wei

2016-02-28

In this study, the influence of the functional groups by the diblock copolymers of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), poly(styrene-b-2-vinylpyridine) (PS-b-P2VP), and poly(styrene-b-methyl methacrylate) (PS-b-PMMA) on their blends with octa-functionalized phenol polyhedral oligomeric silsesquioxane (OP-POSS) nanoparticles (NPs) was investigated. The relative hydrogen bonding strengths in these blends follow the order PS-b-P4VP/OP-POSS > PS-b-P2VP/OP-POSS > PS-b-PMMA/OP-POSS based on the Kwei equation from differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopic analyses. Small-angle X-ray scattering and transmission electron microscopic analyses show that the morphologies of the self-assembly structures are strongly dependent on the hydrogen bonding strength at relatively higher OP-POSS content. The PS-b-P4VP/OP-POSS hybrid complex system with the strongest hydrogen bonds shows the order-order transition from lamellae to cylinders and finally to body-centered cubic spheres upon increasing OP-POSS content. However, PS-b-P2VP/OP-POSS and PS-b-PMMA/OP-POSS hybrid complex systems, having relatively weaker hydrogen bonds, transformed from lamellae to cylinder structures at lower OP-POSS content (50 wt%).

Activity of Antimicrobial Silver Polystyrene Nanocomposites

Directory of Open Access Journals (Sweden)

M. Palomba

2012-01-01

Full Text Available A simple technique based on doping polymers with in situ generated silver nanoparticles (Ag/PS films has been developed. In particular, an antiseptic material has been prepared by dissolving silver 1,5-cyclooctadiene-hexafluoroacetylacetonate in amorphous polystyrene, and the obtained solid solution has been heated for ca. 10 s at a convenient temperature (180°C. Under such conditions the metal precursor decomposes producing silver atoms that diffuse into the polymer and clusterize. The antimicrobial characteristics of the resulting polystyrene-based material have been accurately evaluated toward Escherichia coli (E. coli comparing the cytotoxicity effect of 10 wt.% and 30 wt.% (drastic and mild annealing silver-doped polystyrene to the corresponding pure micrometric silver powder. Two different bacterial viability assays were performed in order to demonstrate the cytotoxic effect of Ag/PS films on cultured E. coli: (1 turbidimetric determination of optical density; (2 BacLight fluorescence-based test. Both methods have shown that silver-doped polystyrene (30 wt.% provides higher antibacterial activity than pure Ag powder, under similar concentration and incubation conditions.

Synthesis of fluorescent diblock copolymer nanoparticle supported ...

Indian Academy of Sciences (India)

2017-06-09

Jun 9, 2017 ... and induction time (Ti) were determined from the UV–visible spectral data. ... The photo- degradation of rhodamine dye was carried out in the presence ... ence of hierarchical structured polystyrene/polyaniline@Au.

Recycling tires? Reversible crosslinking of poly(butadiene).

Science.gov (United States)

Trovatti, Eliane; Lacerda, Talita M; Carvalho, Antonio J F; Gandini, Alessandro

2015-04-01

Furan-modified poly(butadiene) prepared by the thiol-ene click reaction is crosslinked with bismaleimides through the Diels-Alder reaction, giving rise to a novel recyclable elastomer. This is possible because of the thermal reversibility of the adducts responsible for the formation of the network. The use of this strategy provides the possibility to produce recyclable tires. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of glucoamylase immobilization in butadiene nitrile latex membrane

International Nuclear Information System (INIS)

Miller, E.

1992-01-01

Attempts have been undetaken to immobilize glucoamylaze by means of butadiene nitrile latex in the presence of a chemical initiator and 60 Co γ-radiation. The activity, stability of conjugates in the membrane and permeability of oxygen in these membranes were determined. (author) 14 refs.; 5 figs

Supramolecular self-assembly and opto-electronic properties of semiconducting block copolymers

NARCIS (Netherlands)

Boer, Bert de; Stalmach, Ulf; Hutten, Paul F. van; Melzer, Christian; Krasnikov, Victor V.; Hadziioannou, Georges

2001-01-01

With continuous and nanometre-scale interpenetrating phases of electron donor and acceptor components, a novel diblock copolymer, in which one block is poly(p-phenylene vinylene) (PPV) and the other is a C60-functionalized polystyrene, is designed to be an efficient photovoltaic material. The

Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers

Science.gov (United States)

An, Hyosung; Mike, Jared; Smith, Kendall; Swank, Lisa; Lin, Yen-Hao; Pesek, Stacy; Verduzco, Rafael; Lutkenhaus, Jodie

Structural energy storage materials combining load-bearing mechanical properties and high energy storage performance are desired for applications in wearable devices or flexible displays. Vanadium pentoxide (V2O5) is a promising cathode material for possible use in flexible battery electrodes, but it remains limited by low Li+ diffusion coefficient and electronic conductivity, severe volumetric changes upon cycling, and limited mechanical flexibility. Here, we demonstrate a route to address these challenges by blending a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT- b-PEO), with V2O5 to form a mechanically flexible, electro-mechanically stable hybrid electrode. V2O5 layers were arranged parallel in brick-and-mortar-like fashion held together by the P3HT- b-PEO binder. This unique structure significantly enhances mechanical flexibility, toughness and cyclability without sacrificing capacity. Electrodes comprised of 10 wt% polymer have unusually high toughness (293 kJ/m3) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes.

Impact of water chemistry on surface charge and aggregation of polystyrene microspheres suspensions.

Science.gov (United States)

Lu, Songhua; Zhu, Kairuo; Song, Wencheng; Song, Gang; Chen, Diyun; Hayat, Tasawar; Alharbi, Njud S; Chen, Changlun; Sun, Yubing

2018-07-15

The discharge of microplastics into aquatic environment poses the potential threat to the hydrocoles and human health. The fate and transport of microplastics in aqueous solutions are significantly influenced by water chemistry. In this study, the effect of water chemistry (i.e., pH, foreign salts and humic acid) on the surface charge and aggregation of polystyrene microsphere in aqueous solutions was conducted by batch, zeta potentials, hydrodynamic diameters, FT-IR and XPS analysis. Compared to Na + and K + , the lower negative zeta potentials and larger hydrodynamic diameters of polystyrene microspheres after introduction of Mg 2+ were observed within a wide range of pH (2.0-11.0) and ionic strength (IS, 0.01-500mmol/L). No effect of Cl - , HCO 3 - and SO 4 2- on the zeta potentials and hydrodynamic diameters of polystyrene microspheres was observed at low IS concentrations (10mmol/L). The zeta potentials of polystyrene microspheres after HA addition were decreased at pH2.0-11.0, whereas the lower hydrodynamic diameters were observed at pH<4.0. According to FT-IR and XPS analysis, the change in surface properties of polystyrene microspheres after addition of hydrated Mg 2+ and HA was attributed to surface electrostatic and/or steric repulsions. These investigations are crucial for understanding the effect of water chemistry on colloidal stability of microplastics in aquatic environment. Copyright © 2018 Elsevier B.V. All rights reserved.

Dissociative photoionization of 1,3-butadiene: experimental and theoretical insights.

Science.gov (United States)

Fang, Wenzheng; Gong, Lei; Zhang, Qiang; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

2011-05-07

The vacuum-ultraviolet photoionization and dissociative photoionization of 1,3-butadiene in a region ∼8.5-17 eV have been investigated with time-of-flight photoionization mass spectrometry using tunable synchrotron radiation. The adiabatic ionization energy of 1,3-butadiene and appearance energies for its fragment ions, C(4)H(5)(+), C(4)H(4)(+), C(4)H(3)(+), C(3)H(3)(+), C(2)H(4)(+), C(2)H(3)(+), and C(2)H(2)(+), are determined to be 9.09, 11.72, 13.11, 15.20, 11.50, 12.44, 15.15, and 15.14 eV, respectively, by measurements of photoionization efficiency spectra. Ab initio molecular orbital calculations have been performed to investigate the reaction mechanism of dissociative photoionization of 1,3-butadiene. On the basis of experimental and theoretical results, seven dissociative photoionization channels are proposed: C(4)H(5)(+) + H, C(4)H(4)(+) + H(2), C(4)H(3)(+) + H(2) + H, C(3)H(3)(+) + CH(3), C(2)H(4)(+) + C(2)H(2), C(2)H(3)(+) + C(2)H(2) + H, and C(2)H(2)(+) + C(2)H(2) + H(2). Channel C(3)H(3)(+) + CH(3) is found to be the dominant one, followed by C(4)H(5)(+) + H and C(2)H(4)(+) + C(2)H(2). The majority of these channels occur via isomerization prior to dissociation. Transition structures and intermediates for those isomerization processes were also determined.

In-Situ TEM Study of Interface Sliding and Migration in an Ultrafine Lamellar Structure

Energy Technology Data Exchange (ETDEWEB)

Hsiung, L M

2005-12-06

The instability of interfaces in an ultrafine TiAl-({gamma})/Ti{sub 3}Al-({alpha}{sub 2}) lamellar structure by straining at room temperature has been investigated using in-situ straining techniques performed in a transmission electron microscope. The purpose of this study is to obtain experimental evidence to support the creep mechanisms based upon the interface sliding in association with a cooperative movement of interfacial dislocations previously proposed to interpret the nearly linear creep behavior observed from ultrafine lamellar TiAl alloys. The results have revealed that both the sliding and migration of lamellar interfaces can take place simultaneously as a result of the cooperative movement of interfacial dislocations.

How do closed-compact multi-lamellar droplets form under shear flow? A possible mechanism

Science.gov (United States)

Courbin, L.; Pons, R.; Rouch, J.; Panizza, P.

2003-01-01

The formation of closed-compact multi-lamellar droplets obtained upon shearing both a lamellar phase (Lα) and a two-phase separated lamellar-sponge (Lα-L3) mixture is investigated as a function of the shear rate dot gamma, using small-angle light scattering (SALS) and cross-polarized optical microscopy. In both systems the formation of droplets occurs homogeneously in the cell at a well-defined wave vector qe propto dot gamma1/3 via a strain-controlled process. These results suggest that the formation of droplets may be monitored in both systems by a buckling instability of the lamellae as predicted from a recent theory.

Well-defined triblock copolymers of polyethylene with polycaprolactone or polystyrene using a novel difunctional polyhomologation initiator

KAUST Repository

Hadjichristidis, Nikolaos

2017-08-04

α,ω-Dihydroxy polyethylene was synthesized by polyhomologation of dimethylsulfoxonium methylide with 9-thexyl-9-BBN (9-BNN: 9-Borabicyclo[3.3.1]nonane), a novel difunctional initiator produced from 9-BBN and 2,3-dimethylbut-2-ene, with two active and one blocked sites, followed by hydrolysis/oxidation. The terminal hydroxy groups were either used directly as initiators, in the presence of 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-BuP2), for the ring opening polymerization of ɛ-caprolactone to afford polycaprolactone-b-polyethylene-b-polycaprolactone (PCL-b-PE-b-PCL) or after transformation to atom transfer radical polymerization initiating sites, for the polymerization of styrene to produce polystyrene-b-polyethylene-b-polystyrene (PSt-b-PE-b-PSt) triblock copolymers. Molecular characterization by 11B, 13C and 1H NMR as well as FTIR, and high temperature GPC (HT-GPC) confirmed the well-defined nature of the synthesized new difunctional initiator and triblock copolymers. Differential scanning calorimetry was used to determine the melting points of PE and PCL.

Association between lamellar body count and respiratory distress in neonates

International Nuclear Information System (INIS)

Bahasadri, Shoreh; Changizi, Nasrin

2005-01-01

Assessment of fetal lung maturity by a simple and rapid test has a pivotal role in obstetric managements. Lack of modern laboratory techniques in our country made US investigate whether lamellar body count (Lb) can be applied efficiently in the evaluation of fetal lung maturity. Lamellar body count was assessed in 104 un spun amniotic fluid samples taken from pregnant women admitted at A kbar Aba di Hospital, Tehran, Iran between May 2003 and November 2003 whose fetuses were at risk for respiratory distress syndrome (RDS). Cut-off points for LBC were determined to evaluate the risk of RDS. Standard clinical and radiographic criteria were used to diagnose RDS. An LBC of less than 10,000 was 99.1% specific for lung immaturity (positive predictive value = 99.1%, negative predictive value = 83.5%). The LBCs of greater than 45,000 eliminates RDS (negative predictive value = 98.9%). Lamellar body count is an easy, rapid and cost-effective test to assess fetal lung maturity in high-risk fetuses. Using the cut-off points of 10,000 and 45,000, LBC can serve as the first screening test of fetal lung maturity. (author)

Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides

Science.gov (United States)

Bouquillon, Sandrine; Muzart, Jacques; Pinel, Catherine; Rataboul, Franck

The telomerization of butadiene with alcohols is an elegant way to synthesize ethers with minimal environmental impact since this reaction is 100% atom efficient. Besides telomerization of butadiene with methanol and water that is industrially developed, the modification of polyols is still under development. Recently, a series of new substrates has been involved in this reaction, including diols, pure or crude glycerol, protected or unprotected monosaccharides, as well as polysaccharides. This opens up the formation of new products having specific physicochemical properties. We will describe recent advances in this field, focusing on the reaction of renewable products and more specifically on saccharides. The efficient catalytic systems as well as the optimized reaction conditions will be described and some physicochemical properties of the products will be reported.

Effect of salivary secretory IgA on the adhesion of Candida albicans to polystyrene.

Science.gov (United States)

San Millán, R; Elguezabal, N; Regúlez, P; Moragues, M D; Quindós, G; Pontón, J

2000-09-01

Attachment of Candida albicans to plastic materials of dental prostheses or to salivary macromolecules adsorbed on their surface is believed to be a critical event in the development of denture stomatitis. In an earlier study, it was shown that adhesion of C. albicans to polystyrene, a model system to study the adhesion of C. albicans to plastic materials, can be partially inhibited with an mAb directed against cell wall polysaccharides of C. albicans. In the present study, the role of whole saliva in the adhesion of C. albicans to polystyrene has been investigated, and three mAbs directed against epitopes of cell wall mannoproteins have been used to mimic the inhibitory effect observed with salivary secretory IgA (sIgA) on the adhesion of C. albicans to polystyrene. In the absence of whole saliva, adherence of C. albicans 3153 increased with germination. However, the presence of whole saliva enhanced the adhesion to polystyrene of C. albicans 3153 yeast cells but decreased the adhesion of germinated cells. The enhancement of adhesion of yeast cells to polystyrene mediated by saliva was confirmed with an agerminative mutant of C. albicans 3153. The inhibition of the adhesion of C. albicans 3153 germ tubes to polystyrene was due to the salivary sIgA since sIgA-depleted saliva enhanced the adhesion of C. albicans 3153 to polystyrene. The inhibitory effect mediated by sIgA was not related to the inhibition of germination but to the blockage of adhesins expressed on the cell wall surface of the germ tubes. The three mAbs studied reduced the adhesion of C. albicans 3153 to polystyrene at levels equivalent to those for purified sIgA. The highest reduction in the adhesion was obtained with the IgA mAb N3B. The best results were obtained when the three mAbs were combined. The results suggest that whole saliva plays a different role in the adhesion of C. albicans to polystyrene depending on the morphological phase of C. albicans. These results may give new insights into the

Synthesis of micro-sized polystyrene magnetic particles

International Nuclear Information System (INIS)

Neves, Juliete S.; Suarez, Paulo A.Z.; Umpierre, Alexandre P.; Machado, Fabricio; Souza Junior, Fernando G. de

2011-01-01

The present work illustrates the synthesis of spherical and micro-sized polystyrene magnetic particles by using a water-based suspension polymerization process to incorporate in situ surface modified superparamagnetic Fe 3 O 4 nanoparticles. The crystallite size of Fe 3 O 4 was determined to be equal to 7.7 nm, based on Scherrer's equation and XRD measurement. According to EDX analyses, Fe 3 O 4 / polystyrene nanocomposites particles show strong characteristic peaks Kα and Kβ of iron at the interval from 6.38 KeV to 7.04 KeV with an amount of iron in the samples equal to 98 %, indicating that the inorganic material dispersed in the polystyrene matrix is essentially Fe in the form of iron oxide (Fe 3 O 4 ). The obtained polymeric materials presented good magnetic behavior, indicating that the modified Fe 3 O 4 nanoparticles were successfully dispersed in the polystyrene particles. (author)

Synthesis of novel nitroso acetal derivatives via tandem 6π-electrocyclization/ [3+2]-cycloaddition of 1-nitro-2-methyl-1,3 butadiene

OpenAIRE

Esra Koc

2017-01-01

Novel nitroso acetal derivatives (4-methyl-2,3,3a,6-tetrahydroisoxazolo[2,3-b][1,2]oxazine) were synthesized through 6π-electrocyclization/[3+2]-cycloaddition reaction of several dionophiles with 1-nitro-2-methyl-1,3-butadiene. Structures of the synthesized compounds were determined by 1H-NMR, 13C-NMR, IR and GC-MS analyses.

Creep characteristics of a hypoeutectic Mg-Ca binary alloy with a near-fully lamellar microstructure

International Nuclear Information System (INIS)

Terada, Yoshihiro; Tsukahara, Masashi; Shibayama, Atsushi; Murata, Yoshinori; Morinaga, Masahiko

2011-01-01

Highlights: → We develop a hypoeutectic Mg-Ca cast alloy with a near-fully lamellar microstructure. → Dislocations are introduced within the lamellar microstructure during casting. → The dislocation segments in the α-Mg plates are located on the basal planes. → Creep of the alloy is ascribed to the easy glide of the introduced dislocations. -- The creep behavior of a hypoeutectic Mg-14.8 mass% Ca cast alloy with an α-Mg/C14-Mg 2 Ca near-fully lamellar microstructure was investigated at 473 K. Transmission electron microscopy shows that dislocations are introduced within the lamellar microstructure of the alloy during casting; the dislocation segments in the α-Mg plates are located on basal planes. The stress exponent of the creep rate is unity in the early stage of transient creep. Creep deformation of the alloy is ascribed to the easy glide of the introduced dislocations.

A Case Report of Ichthyosis Lamellar Syndrome

Directory of Open Access Journals (Sweden)

Gh. Eshghi

2014-04-01

Full Text Available Introduction: Ichthyosis lamellar syndrome is a rare genodermatosis and in most families is inherited as an autosomal recessive trait because of transglutaminase-1 deficiency. Case Report: Our patient was a 6 year old girl and she was the result of consanguinity. She had large plate-like scales. The scales had mosaic-like pattern and erythroderma was absent. Tautness of her facial skin was associated with ectropion and eclabion and hypoplasia of auricular cartilages. She had scarring alopecia because of taut skin (specially at the periphery of scalp. She also had palmoplantar keratoderma and secondary nail dystrophy and thanked nails. Her parents also gave us the history of heat intolerance and it is because of interaepi-dermal constriction of sweat ducts. Our patient had the history of recurrent ear infections and it is because of accumulation of scales in the external ear. Conclusion: Our patient underwent a biopsy and based on our clinical findings her diagnosis was lamellar ichthyosis. (Sci J Hamadan Univ Med Sci 2014; 21 (1:76-79

Technical Note: Effect of Incorporating Expanded Polystyrene ...

African Journals Online (AJOL)

Incorporating expanded polystyrene granules in concrete matrix can produce lightweight polystyrene aggregate concrete of various densities. Workability which is an important property of concrete, aects the rate of placement and the degree of compaction of concrete. Inadequate compaction leads to reduction in both ...

Complications and Management of Deep Anterior Lamellar Keratoplasty

Directory of Open Access Journals (Sweden)

Banu Torun Acar

2014-10-01

Full Text Available Objectives: To report the intraoperative and postoperative follow-up complications and management of these in deep anterior lamellar keratoplasty (DALK surgery. Materials and Methods: Two hundred eighty-four eyes of 252 patients followed up in our cornea clinic who underwent DALK using Anwar’s big-bubble technique with healthy Descemet’s membrane and endothelium were included in this study. Intraoperative and postoperative complications as well as the management and treatment of these complications were evaluated. Results: Big bubble was created in 220 (77.5% eyes of 284 eyes, and lamellar dissection was performed in 64 (22.5% eyes. Perforation occurred during trephination in 4 eyes, and the procedure was accomplished by penetrating keratoplasty (PK. Intraoperative microperforation occurred in 44 eyes. Perforation enlarged in 4 eyes and PK was performed. Operation was continued in 40 eyes with air injection into the anterior chamber. In postopertive follow-up period, double anterior chamber (DAC occurred in 32 of 40 eyes. DAC spontaneously regressed in 8 eyes, and air was given into the anterior chamber with a second surgical intervention in 24 eyes. DAC improved in 20 eyes. Four eyes underwent PK. Fungal keratitis evolved at the interface in one eye, because of no healing during the follow-up period, this eye underwent PK under antifungal therapy. Eyes with interface haze and Descemet’s membrane folds were followed. Conclusion: DALK is a difficult technique with a steep learning curve. In addition to the complications seen in PK, specific complications can occur in lamellar surgery. (Turk J Ophthalmol 2014; 44: 337-40

Diffuse lamellar keratitis after laser in situ keratomileusis with the Moria LSK-One and Carriazo-Barraquer microkeratomes.

Science.gov (United States)

Thammano, Pavika; Rana, Azhar N; Talamo, Jonathan H

2003-10-01

To assess risk factors for and incidence of diffuse lamellar keratitis (DLK) and to investigate whether microkeratome design is associated with the incidence of DLK. The Laser Eye Consultants of Boston, Boston and Waltham, Massachusetts, USA. In a retrospective nonrandomized comparative study, 1122 consecutive primary laser in situ keratomileusis (LASIK) treatments (584 patients) were analyzed to determine the incidence of DLK using 2 different microkeratome designs (Moria LSK-One [LSK] and Moria Carriazo-Barraquer [C-B]). The incidence of DLK was as determined by clinical signs. The overall incidence of DLK was 2.23%. The incidence in the LSK and C-B groups was 1.09% and 4.38%, respectively, with a statistically significant difference in incidence between the 2 groups (P<.01). Epithelial irregularities increased the risk for DLK. There was no significant statistical difference in sex, age, operating room location, type of laser, or time of day the surgery was performed between the 2 groups or between eyes that had DLK and eyes without DLK. The incidence of DLK using the C-B microkeratome fell significantly after May 2000, when new cleaning methods for this device were introduced. Different microkeratomes and how they are maintained may influence the incidence of DLK. Diffuse lamellar keratitis is more common after LASIK in a setting of epithelial irregularities, whether or not an actual epithelial defect is created.

A structural study of lamellar phases formed by nucleoside-functionalized lipids

Energy Technology Data Exchange (ETDEWEB)

Berti, D.; Fratini, E.; Baglioni, P. [Department of Chemistry and CSGI, University of Florence, Via G. Capponi 9, 50121 Florence (Italy); Dante, S.; Hauss, T. [Berlin Neutron Scattering Center, Hahn Meitner Institut, Glienicker Strasse 100, Wannsee, 14109 Berlin (Germany)

2002-07-01

We report a neutron-scattering investigation of lamellar phases formed by novel phospholipids bearing nucleosides at the polar-head-group region. These nucleolipids can interact through stacking and H-bond interactions, following a pattern that resembles base-base coupling in natural nucleic acids (DNA, RNA), i.e. they have similar recognition properties. Bilayer stacks formed of DPP-adenosine, DPP-uridine and their 1:1 mixture were investigated after equilibration in a 98% relative humidity atmosphere. The DPP-adenosine spectrum can be accounted for (in analogy to DPPC) by a lamellar phase with a smectic period of about 60 A. DPP-uridine displays a not so straightforward behavior that we have tentatively ascribed to the coexistence of lamellae with different smectic periods. In the 1:1 mixture the lamellar mesophase of DPP-uridine is retained, suggesting a specific interaction of the uridine polar-head group with the adenosine moiety of DPP-adenosine. It should be stressed that this behavior can be considered as an indication of the recognition process occurring at the polar-head-group region of the mixed phospholiponucleoside membrane. (orig.)

Polystyrene calorimeter for electron beam dose measurements

DEFF Research Database (Denmark)

Miller, A.

1995-01-01

Calorimeters from polystrene have been constructed for dose measurement at 4-10 MeV electron accelerators. These calorimeters have been used successfully for a few years, and polystyrene calorimeters for use at energies down to 1 MeV and being tested. Advantage of polystyrene as the absorbing...

Structural studies of lamellar surfactant systems under shear

DEFF Research Database (Denmark)

Mortensen, K.

2001-01-01

Recent experimental studies on concentrated surfactant systems are reviewed. Particular attention is focused on the transformation from planar lamellar sheets to multilamellar vesicles. It is discussed whether both of these states are thermodynamic stable, or if the MLV is an artifact of shear in...

Ameliorating Hemorheology by Direct Hemoperfusion with a Polymyxin B-immobilized Adsorbent

Institute of Scientific and Technical Information of China (English)

Li Yuan; Wang Xiang; Gao Wei; Cai Shaoxi

2004-01-01

Direct hemoperfusion (DHP) with an adsorbent column using polymyxin B-immobilized polystyrene beads has been used to investigate the changes of hemorheology in rabbits with endotoxemia. We measured whole blood viscosity and hemotocrit before and after DHP with polymyxin B-immobilized polystyrene beads. Reduction in blood endotoxin concentration by DHP therapy positively correlated with improvement in hemorheological indexs. Our findings indicate that the amelioration in hemorheology was related directly to endotoxin removal by the adsorbent column with polymyxin B-immobilize polystyrene beads. So DHP with polymyxin B-immobilized polystyrene beads seems to be an important therapeutic strategy for endotoxemia.

Fabrication of polystyrene porous films with gradient pore structures

International Nuclear Information System (INIS)

Yan Hongwei; Zhang Lin; Li Bo; Yin Qiang

2010-01-01

Silica opals and multilayer heterostructures were fabricated by vertical deposition technique. Polystyrene inverse opals and gradient porous structures were obtained by colloidal templating, in order to control the pore microstructure of polymer porous materials. As shown in the scanning electron microscopy images, the polystyrene porous structures are precise replicas of inverse structures of the original templates. After being infiltrated with the polystyrene, the photonic stop-band position of the opal composite is redshifted compared with the original template, and it is blueshifted after the opal template being removed. The filling ratio of polystyrene was calculated according to the Bragg formula. (authors)

Preparation and characterization of zinc sulphide nanocomposites based on acrylonitrile butadiene rubber

Science.gov (United States)

Ramesan, M. T.; Nihmath, A.; Francis, Joseph

2013-06-01

Rubber composite based on acrylonitrile butadiene rubber (NBR) reinforced with nano zinc sulphide (ZnS) have been prepared via vulcanization process and characterized by several techniques. Processing characteristics such as scorch time, optimum cure time decreases with increase in concentration of nano filler in acrylonitrile butadiene rubber. Mechanical properties such as tensile and tear strength increases with increase in concentration of nano filler up to 7 phr of loading thereafter the value decreases, whereas hardness, and flame resistance increases with the dosage of fillers. These enhanced properties are due to the homogenous dispersion of nano fillers in NBR matrix, which is evidenced from the structure that evaluated using X-ray diffraction (XRD) and scanning electron microscopy (SEM).

Incorporation of poly-saccharidic derivatives in model biological systems: monolayers, lamellar phases and vesicles

International Nuclear Information System (INIS)

Deme, Bruno

1995-01-01

Our aim is to introduce a soluble polymer in a lyotropic lamellar phase, and to modify the force balance in the case of a collapsed system where no repulsive contribution overcomes the van der Waals attraction, except at very short distances where hydration forces dominate (i.e. a collapsed stack of membranes). Mixed layers of a synthetic lecithin (DMPC) and a hydrophobically modified polysaccharide (cholesteryl-pullulan, CHP) have been investigated at the air-water interface by surface tension experiments and by specular reflection of neutrons. The DMPC/CHP/water ternary phase diagram has been determined by small angle X-ray scattering (SAXS) and small angle neutron scattering (SANS). CHP derivatives are associative polymers bearing lateral cholesterol groups that interact with a polar phases such as phospholipid monolayers and biological membranes. These derivatives are surface active and self-aggregate in solution leading to the formation of soluble micellar type aggregates. The interaction of CHP derivatives with lipidic structures involves the anchoring of the cholesterol groups that yields to the tethering of the poly-saccharidic backbones at lipid/water interfaces. These poly-saccharidic backbones are flexible chains in good solvent in water. Using these derivatives and a new preparation procedure, we show that it is possible to avoid the depletion of the polysaccharide due to its steric exclusion by the collapsed DMPC lamellar phase. We are able to prepare samples at thermodynamic equilibrium with the polysaccharide solubilized in the lamellar phase, a situation opposed to the well known behavior of mixed polysaccharide/lecithin Systems commonly used in osmotic stress experiments. Here, the osmotic pressure of the chains confined in the lamellar lattice acts as a new long range repulsive contribution in the DMPC lyotropic L_α phase and results in the swelling of the lamellar phase at large membrane separations (570 A). Such bilayer separations allow out of

Incidental Finding of Lamellar Calcification of the Falx Cerebri Leading to the Diagnosis of Gorlin-Goltz Syndrome

Directory of Open Access Journals (Sweden)

I. Saulite

2013-10-01

Full Text Available Here, we report the case of an incidental finding of lamellar calcification of the falx cerebri in a routine computed tomography scan of the head after an accidental trauma. This lamellar calcification led to the diagnosis of Gorlin-Goltz syndrome (GGS in the patient and her daughter. Lamellar calcification of the falx cerebri is a pathognomonic feature of GGS. Our case report highlights the importance of a multidisciplinary diagnostic approach to GGS.

Incidental finding of lamellar calcification of the falx cerebri leading to the diagnosis of gorlin-goltz syndrome.

Science.gov (United States)

Saulite, I; Voykov, B; Mehra, T; Hoetzenecker, W; Guenova, E

2013-01-01

Here, we report the case of an incidental finding of lamellar calcification of the falx cerebri in a routine computed tomography scan of the head after an accidental trauma. This lamellar calcification led to the diagnosis of Gorlin-Goltz syndrome (GGS) in the patient and her daughter. Lamellar calcification of the falx cerebri is a pathognomonic feature of GGS. Our case report highlights the importance of a multidisciplinary diagnostic approach to GGS.

Effect of field cooling heights on the levitation force of pure and starch/polystyrene/MWCNT added bulk MgB{sub 2} superconductors

Energy Technology Data Exchange (ETDEWEB)

Tripathi, D.; Dey, T.K., E-mail: tapasdey@hijli.iitkgp.ernet.in

2014-12-15

Highlights: • Levitation force between PM and starch/PS/MWCNT added MgB{sub 2} are studied in FC mode. • MgB{sub 2} added with 1 wt.% PS gives best result. • Levitation forces do not display hysteresis during ascending and descending mode. • Exponential variation in Max. Levitation (F{sub MLF}) and attractive forces (F{sub MAF}). • The gap between PM and SC for F{sub MAF} and F{sub 0AF} varies linearly with FC height. - Abstract: A series of MgB{sub 2} pellets with and without addition of carbon from different sources (viz. starch, polystyrene and carbon nanotubes) have been synthesized by solid state reaction under argon atmosphere. XRD analysis indicates a decrease in lattice parameters of MgB{sub 2} with addition of starch, polystyrene (PS) and MWCNT and confirms substitution of carbon in boron sites. The presence of nanosized carbon inclusions between the grain boundaries in the present set of samples is evident in TEM photographs. Resistivity data confirms a decrease in superconducting transition temperature (T{sub c0}) for MgB{sub 2} doped with starch/PS/MWCNT. The effect of different field cooling heights (H{sub IFC}) at 20 K on maximum levitation force (F{sub MLF}) and maximum attractive force (F{sub MAF}) of pure MgB{sub 2} and MgB{sub 2} doped with starch/PS/MWCNT have been investigated. Except for MWCNT, doping of starch and PS in MgB{sub 2} is found to improve F{sub MLF} and F{sub MAF} and the best result is obtained for MgB{sub 2} doped with 1 wt.% PS. Levitation force measured as a function of decreasing initial field cooling height indicates exponential dependence of both maximum levitation force (F{sub MLF}) and maximum attractive force (F{sub MAF}). However, the gap distance between PM and the sample (H{sub 0AF} and H{sub MAF}) corresponding to maximum attractive force (F{sub MAF}) and zero attractive force (F{sub 0AF}) varies linearly and their difference remains constant. This constancy in (H{sub MAF} − H{sub 0AF}) is understood in

The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents.

Science.gov (United States)

Mojica, Martha; Méndez, Francisco; Alonso, Julio A

2016-02-12

The Diels-Alder (DA) reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs). The density functional theory (DFT) B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1) and pentacyclopentacorannulene (pristine hemifullerene 2), could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH₂, OMe, OH, Me, i-Pr) and electron-withdrawing groups (F, COOH, CF₃, CHO, CN, NO₂). The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO₂ substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

Finite element analysis for the initiation of lamellar tearing in welded joints

International Nuclear Information System (INIS)

Krieg, R.D.; Thomas, R.K.

1980-01-01

A numerical procedure using the finite element method is presented for predicting the initiation of lamellar tearing in fillet welded T-joints commonly employed in large structures. Starting with a prescribed geometry, the welding process is approximated by a known time-dependent volumetric heat source which simulates the arc heating and deposition of liquid metal. The transient nonlinear thermal and stress problems are then solved using finite element computer codes. Results of the elastic-plastic stress analysis are presented showing a predicted region of incipient lamellar tearing based on a ductile fracture theory which qualitatively agrees with the size and location of tears typically observed in photomicrographs. Additional insight into post failure crack length and stability is presented based on a simplified linear elastic fracture mechanics approach. Although the analysis procedure shows signs of promise, several weak points in the model are pointed out which must be improved before lamellar tearing can be quantified in an approach of this general type

Direct Visualisation of the Structural Transformation between the Lyotropic Liquid Crystalline Lamellar and Bicontinuous Cubic Mesophase.

Science.gov (United States)

Tran, Nhiem; Zhai, Jiali; Conn, Charlotte E; Mulet, Xavier; Waddington, Lynne J; Drummond, Calum J

2018-05-29

The transition between the lyotropic liquid crystalline lamellar and the bicontinuous cubic mesophase drives multiple fundamental cellular processes involving changes in cell membrane topology including endocytosis and membrane budding. While several theoretical models have been proposed to explain this dynamic transformation, experimental validation of these models has been challenging due to the short lived nature of the intermediates present during the phase transition. Herein, we report the direct observation of a lamellar to bicontinuous cubic phase transition in nanoscale dispersions using a combination of cryogenic transmission electron microscopy and static small angle X-ray scattering. The results represent the first experimental confirmation of a theoretical model which proposed that the bicontinuous cubic phase originates from the centre of a lamellar vesicle, then propagates outward via the formation of inter-lamellar attachments and stalks. The observation was possible due to the precise control of the lipid composition to place the dispersion systems at the phase boundary of a lamellar and a cubic phase, allowing for the creation of long-lived structural intermediates. By surveying the nanoparticles using cryogenic transmission electron microscopy, a complete phase transition sequence was established.

Lamellar γ-AlOOH architectures: Synthesis and application for the removal of HCN

International Nuclear Information System (INIS)

Hou Hongwei; Zhu You; Tang Gangling; Hu Qingyuan

2012-01-01

Using hexadecyl trimethyl ammonium bromide (CTAB) as a structure-directing agent and precipitator, the complete synthesis of lamellar γ-AlOOH architectures was successfully accomplished via a hydrothermal route. Different product structures were obtained by varying the molar ratio of aluminum nitrate and CTAB. Several techniques, including X-ray powder diffraction, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry thermal analysis, were used to characterize the products. The effects of CTAB concentration, reaction temperature and time, and the molar ratio of Al 3+ /CTAB on the product morphologies were investigated. The nitrogen adsorption and desorption measurements indicated that the γ-AlOOH architectures possess a Brunauer–Emmett–Teller surface area of approximately 75.02 m 2 /g. It was also demonstrated that 10 mg γ-AlOOH architectures can remove 45.3% of the HCN (1.68 μg/mL) from model wastewater. When 0.03 mg/cig γ-AlOOH architectures were combined with cigarette paper, 8.12% of the present HCN was adsorbed. These results indicate that lamellar γ-AlOOH architectures may be a potential adsorbent for removing HCN from highly toxic pollutant solutions and harmful cigarette smoke. Highlights: ► Hexadecyl trimethyl ammonium bromide (CTAB) was used as a structure-directing agent and precipitator. ► Hydrothermal treatment enables growth of lamellar γ-AlOOH architectures. ► Lamellar γ-AlOOH architectures were demonstrated to exhibit high BET surface area and excellent adsorptive capacity. ► HCN in contaminated water and cigarette smoke can be effectively removed by the prepared lamellar γ-AlOOH superstructures.

Seeded emulsion polymerization of butadiene. 1. The propagation rate coefficient

NARCIS (Netherlands)

Verdurmen, E.M.F.J.; Dohmen, E.H.M.; Verstegen, J.M.; Maxwell, I.A.; German, A.L.; Gilbert, R.G.

1993-01-01

The kinetics of the emulsifier-free, seeded polymn. of butadiene (I) at 60 Deg in Smith-Ewart interval III were studied in presence of Na peroxodisulfate initiator and tert-dodecyl mercaptan. The fractional conversion was based on gravimetrically calibrated online densitometry and was highly

The Plumber’s Nightmare Phase in Diblock Copolymer/Homopolymer Blends. A Self-Consistent Field Theory Study.

KAUST Repository

Martinez-Veracoechea, Francisco J.; Escobedo, Fernando A.

2009-01-01

Using self-consistent field theory, the Plumber's Nightmare and the double diamond phases are predicted to be stable in a finite region of phase diagrams for blends of AB diblock copolymer (DBC) and A-component homopolymer. To the best of our

One- and two-dimensional fluids properties of smectic, lamellar and columnar liquid crystals

CERN Document Server

Jakli, Antal

2006-01-01

Smectic and lamellar liquid crystals are three-dimensional layered structures in which each layer behaves as a two-dimensional fluid. Because of their reduced dimensionality they have unique physical properties and challenging theoretical descriptions, and are the subject of much current research. One- and Two-Dimensional Fluids: Properties of Smectic, Lamellar and Columnar Liquid Crystals offers a comprehensive review of these phases and their applications. The book details the basic structures and properties of one- and two-dimensional fluids and the nature of phase transitions. The later chapters consider the optical, magnetic, and electrical properties of special structures, including uniformly and non-uniformly aligned anisotropic films, lyotropic lamellar systems, helical and chiral structures, and organic anisotropic materials. Topics also include typical and defective features, magnetic susceptibility, and electrical conductivity. The book concludes with a review of current and potential applications ...

A self-consistent field study of diblock copolymer/charged particle system morphologies for nanofiltration membranes

International Nuclear Information System (INIS)

Zhang, Bo; Ye, Xianggui; Edwards, Brian J.

2013-01-01

A combination of self-consistent field theory and density functional theory was used to examine the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Both neutral and interacting particles were examined, with and without favorable/unfavorable energetic potentials between the particles and the block segments. The phase diagrams of the various systems were constructed, allowing the identification of three types of ordered mesophases composed of lamellae, hexagonally packed cylinders, and spheroids. In particular, we examined the conditions under which the mesophases could be generated wherein the tethered particles were primarily located within the interface between the two blocks of the copolymer. Key factors influencing these properties were determined to be the particle position along the diblock chain, the interaction potentials of the blocks and particles, the block copolymer composition, and molecular weight of the copolymer

A reactive polystyrene-block-polyisoprene star copolymer as a toughening agent in an epoxy thermoset

KAUST Repository

Francis, Raju; Baby, Deepa K.

2015-01-01

© 2015 Springer-Verlag Berlin Heidelberg A polystyrene-block-polyisoprene ((PS-b-PI)3) star polymer was synthesized by photochemical reversible addition fragmentation chain transfer (RAFT) polymerization. The obtained star polymer was epoxidized

Pengaruh Penggunaan Nitril Butadiene Rubber Dan Pale Crepe Pada Pembuatan Sol Karet Untuk Sepatu Pengaman

OpenAIRE

Yuniari, Arum

2010-01-01

Rubber sole for safety shoes was different on physical specification with general sole, especially on abrasion resistance and oil resistance. The objective of the study was to determine the effect of nitril butadiene rubber and pale crepe on physical properties of vulcanized rubber sole for safety shoes. Rubber sole for safety shoes was produced by blending pale crepe and nitril butadiene rubber with ratio of : 50/50; 60/40; 70/30 and 80/20 phr, respectively. Carbon black as filler was also v...

Pengaruh penggunaan nitril butadiene rubber dan pale crepe pada pembuatan sol karet untuk sepatu pengaman

OpenAIRE

Arum Yuniari

2010-01-01

Abstract Rubber sole for safety shoes was different on physical specification with general sole, especially on abrasion resistance and oil resistance. The objective of the study was to determine the effect of nitril butadiene rubber and pale crepe on physical properties of vulcanized rubber sole for safety shoes. Rubber sole for safety shoes was produced by blending pale crepe and nitril butadiene rubber with ratio of : 50/50; 60/40; 70/30 and 80/20 phr, respectively. Carbon black as fill...

Influence of recycled polystyrene beads on cement paste properties

Directory of Open Access Journals (Sweden)

Maaroufi Maroua

2018-01-01

Full Text Available In order to keep up with the requirements of sustainable development, there is a growing interest towards reducing the energy consumption in the construction and rehabilitation of buildings and the promotion of recycling waste in building materials. The use of recycled polystyrene beads in cement-based materials composition constitutes a solution to improve the insulation in buildings. This allows also limiting landfill by reusing the polystyrene waste. The aim of this study is to compare some properties and performances of a cement paste containing polystyrene beads to a reference paste designed with only the same cement. An experimental campaign was conducted and the obtained results showed that adding recycled polystyrene beads to a cement paste improves its hygro-thermal properties. Further studies are however necessary to better understand the real role of the polystyrene beads in the heat and mass transfers.

In situ cyclization modification in polymerization of butadiene by rare earth coordination catalyst

International Nuclear Information System (INIS)

Wang Chaoyang

2005-01-01

Butadiene was polymerized to a certain extent in the presence of a rare earth coordination catalyst, neodymium compound of neodymium chloride and i-propyl alcohol and triethyl aluminum (NdCl 3 ·3i-PrOH-AlEt 3 ) in toluene and the allyl chloride was then added to the reactive solution in order to in situ cyclize the formed polybutadiene and cyclopolymerize the unreacted butadiene monomers. Effects of molar ratio of allylchloride to AlEt 3 (Cl/Al), cyclization reaction time and temperature, butadiene and NdCl 3 ·3i-PrOH concentrations on the cyclization reaction have been investigated. The cyclization reaction is very quick, only several minutes. The cyclization reaction temperature has few effects on the properties of the cyclized product. Cl/Al is a very important condition for this reaction system. Cyclized polybutadiene has a low value of intrinsic viscosity, free gelling and high yield at high Cl/Al. The microstructures and properties of the cyclized products have been characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and gel permeation chromatography. The cyclization mechanism is put forward

Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and ...

Indian Academy of Sciences (India)

Polyhalogenated-2-nitro-1, 3-butadienes are important synthetic precursors for a variety of poly- functionalized ... biodegradation of morpholine with strains of Mycobac- terium or ...... pounds from very simple precursor in a one-pot ope- ration.

Synthesis and properties of butadiene-alpha-methylstyrene thermoplastic elastomer

Directory of Open Access Journals (Sweden)

A. V. Firsova

2016-01-01

Full Text Available Butadiene-α-methylstyrene block – copolymer – a thermoplastic elastomer (TPE-R DMST occupies a special place among the ethylene – vinyl aromatic block copolymers. TPE-R DMST comprising as plastic – poly-α-methylstyrene unit and elastic – polybutadiene block. TPE-R DMST has high heat resistance, flexibility, abrasion resistance compared to butadiene-styrene thermoplastic elastomer (TPE DST. The synthesis of block copolymers of butadiene and α-methylstyrene was carried out. The process of polymerization the α-methylstyrene characterized the high speed of polymerization in polar medium and low reaction speed in hydrocarbon solvents. Anionic catalyst nbutyllithium (n-BuLi and high concentration – 60–80% α-methylstyrene in the mixture influenced by synthesis of the 1st block of TPE-R DMST, it’s technologically difficult. Found that the low temperature of polymerization α-methylstyrene (+61 o C, the reversibility of these reactions and the high concentration of residual monomer are very importance. It was revealed that a high polymerization rate α-methylstyrene can be achieved by conducting the reaction in a hydrocarbon solvent with polar additives compounds such as tetrahydrofuran (THF and methyl tert-butyl ether (MTBE. The conditions for the synthesis of P-DMST were developed. The kinetics of polymerization for the first DMST-P unit was obtained. Analysis of physical and mechanical properties DMST-P samples was conducted. The optimum content of bound α-methylstyrene block copolymer provides a good combination of properties in a relatively wide temperature range. The tensile strength at normal and elevated temperatures, the hardness and the stiffness of the polymer increased by increasing the content of bound α-methylstyrene. The elongation and the elasticity reduced by increasing the content of bound α-methylstyrene.

A UniChem and electron momentum spectroscopy investigations into the valence electronic structure of trans 1,3 butadiene

Energy Technology Data Exchange (ETDEWEB)

Michalewicz, M.T. [CSIRO, Supercomputing Support Group, Carlton, VIC (Australia). Division of Information Technology; Winkler, D.A. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Clayton, VIC (Australia). Div. of Chemical Physics; Brunger, M.J.; McCarthy, L.E. [Flinders Univ. of South Australia, Bedford Park, SA (Australia). School of Physical Sciences; Von Niessen, W. [Flinders Univ. of South Australia, Bedford Park, SA (Australia). School of Physical Sciences

1996-09-01

The experimental (e,2e) coincidence spectroscopy, known as electron momentum spectroscopy (EMS) was applied to the trans 1,3 butadiene (C{sub 4}H{sub 6}) molecule with detailed binding energy spectra and orbital momentum distributions (MDs) being measured. A small selection of this data is presented. The usage of UniChem computational chemistry codes for the Flinders-developed AMOLD program allows to calculate theoretical MDs for each orbital, to help elucidate the valence electronic structure of butadiene. The results of the many-body Green`s function calculation is also presented, to the ADC(3) level, for the binding energies and spectroscopic factors of the respective orbitals of C{sub 4}H{sub 6}. A critical comparison between the experimental and theoretical MDs allows to determine the optimum wavefunction from the basis sets studied. The determination of the wavefunction then allows to make further use of the UniChem package to derive butadiene`s chemically interesting molecular properties. A summary of these results and comparison of them with the previous results of other workers is presented. 23 refs., 2 tabs., 2 figs.

Molecular modeling and simulation of atactic polystyrene/amorphous silica nanocomposites

International Nuclear Information System (INIS)

Mathioudakis, I; Vogiatzis, G G; Tzoumanekas, C; Theodorou, D N

2016-01-01

The local structure, segmental dynamics, topological analysis of entanglement networks and mechanical properties of atactic polystyrene - amorphous silica nanocomposites are studied via molecular simulations using two interconnected levels of representation: (a) A coarse - grained level. Equilibration at all length scales at this level is achieved via connectivity - altering Monte Carlo simulations. (b) An atomistic level. Initial configurations for atomistic Molecular Dynamics (MD) simulations are obtained by reverse mapping well- equilibrated coarse-grained configurations. By analyzing atomistic MD trajectories, the polymer density profile is found to exhibit layering in the vicinity of the nanoparticle surface. The dynamics of polystyrene (in neat and filled melt systems) is characterized in terms of bond orientation. Well-equilibrated coarse-grained long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm. Atomistic simulation results for the mechanical properties are compared to the experimental measurements and other computational works. (paper)

Thermally Stable Gold Nanoparticles with a Crosslinked Diblock Copolymer Shell

Science.gov (United States)

Jang, Se Gyu; Khan, Anzar; Hawker, Craig J.; Kramer, Edward J.

2010-03-01

The use of polymer-coated Au nanoparticles prepared using oligomeric- or polymeric-ligands tethered by Au-S bonds for incorporation into block copolymer templates under thermal processing has been limited due to dissociation of the Au-S bond at T > 100^oC where compromises their colloidal stability. We report a simple route to prepare sub-5nm gold nanoparticles with a thermally stable polymeric shell. An end-functional thiol ligand consisting of poly(styrene-b-1,2&3,4-isoprene-SH) is synthesized by anionic polymerization. After a standard thiol ligand synthesis of Au nanoparticles, the inner PI block is cross-linked through reaction with 1,1,3,3-tetramethyldisiloxane. Gold nanoparticles with the cross-linked shell are stable in organic solvents at 160^oC as well as in block copolymer films of PS-b-P2VP annealed in vacuum at 170^oC for several days. These nanoparticles can be designed to strongly segregate to the PS-P2VP interface resulting in very large Au nanoparticle volume fractions φp without macrophase separation as well as transitions between lamellar and bicontinuous morphologies as φp increases.

The Electrochemical Assembly of Semiconducting Organic-Inorganic Lamellar Domains for Photovoltaics

Science.gov (United States)

Herman, David John

This dissertation investigates the one-step electrodeposition of alternating nanoscale domains of n-type ZnO and p-type organic molecules for photovoltaics. In such hybrid photovoltaic systems, a nanoscale lamellar periodicity of 5-10 nm between electron donor and electron acceptor materials is ideal for efficient exciton separation. In addition, achieving uniform density and substrate-wide alignment of the hybrid lamellar structures with orientation perpendicular to substrate surfaces is important in providing direct pathways for charge carriers to the electrodes. To this end, it is first reported how to control the assembly of the pyrene-based surfactant 1-pyrenebutyric acid (PyBA) with zinc hydroxide (a precursor to the semiconductor ZnO), resulting in a nanoscale lamellar structure with a periodicity of 3.2 nm. By exploring solution chemistry parameters, the surfactant concentration and solvent composition are shown to have the greatest effect on the morphology of lamellar growth. By studying the early nucleation and growth on indium tin oxide (ITO) substrates with 2D grazing incidence small angle X-ray scattering, it is revealed that the lamellae preferentially nucleate parallel to the hydrophilic ITO surface. It is hypothesized that the conductive and more hydrophobic poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) surface increases the affinity for the pyrene functions to the surface, and therefore the oriented growth of the lamellae changes from parallel to perpendicular with respect to the substrate surface. The second part of this thesis investigates the effects of conjugated surfactant design in directing the growth of hybrid lamellar structures by incorporating either a pyrene or terthiophene moiety and varying overall molecular design. It is found that high aspect ratio and amphiphilic surfactants possessing a flexible alkyl spacer between the carboxylic acid and conjugated moiety consistently allow for the controlled and directed

Morphology in binary blends of poly(vinyl methyl ether) and epsilon-caprolactone-trimethylene carbonate diblock copolymer

NARCIS (Netherlands)

Luyten, MC; Bogels, EJF; vanEkenstein, GORA; tenBrinke, G; Bras, W; Komanschek, BE; Ryan, AJ

The morphology of symmetric diblock copolymer of epsilon-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

Morphology in binary blends of poly(vinyl methyl ether) and ε-caprolactone-trimethylene carbonate diblock copolymer

NARCIS (Netherlands)

Luyten, M.C.; Bögels, E.J.F.; Alberda van Ekenstein, G.O.R.; Brinke, G. ten; Bras, W.; Komanschek, B.E.; Ryan, A.J.

1997-01-01

The morphology of symmetric diblock copolymer of ε-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

In situ ultrahigh-resolution optical coherence tomography characterization of eye bank corneal tissue processed for lamellar keratoplasty.

Science.gov (United States)

Brown, Jamin S; Wang, Danling; Li, Xiaoli; Baluyot, Florence; Iliakis, Bernie; Lindquist, Thomas D; Shirakawa, Rika; Shen, Tueng T; Li, Xingde

2008-08-01

To use optical coherence tomography (OCT) as a noninvasive tool to perform in situ characterization of eye bank corneal tissue processed for lamellar keratoplasty. A custom-built ultrahigh-resolution OCT (UHR-OCT) was used to characterize donor corneal tissue that had been processed for lamellar keratoplasty. Twenty-seven donor corneas were analyzed. Four donor corneas were used as controls, whereas the rest were processed into donor corneal buttons for lamellar transplantation by using hand dissection, a microkeratome, or a femtosecond laser. UHR-OCT was also used to noninvasively characterize and monitor the viable corneal tissue immersed in storage medium over 3 weeks. The UHR-OCT captured high-resolution images of the donor corneal tissue in situ. This noninvasive technique showed the changes in donor corneal tissue morphology with time while in storage medium. The characteristics of the lamellar corneal tissue with each processing modality were clearly visible by UHR-OCT. The in situ characterization of the femtosecond laser-cut corneal tissue was noted to have more interface debris than shown by routine histology. The effects of the femtosecond laser microcavitation bubbles on the corneal tissue were well visualized at the edges of the lamellar flap while in storage medium. The results of our feasibility study show that UHR-OCT can provide superb, in situ microstructural characterization of eye bank corneal tissue noninvasively. The UHR-OCT interface findings and corneal endothelial disc thickness uniformity analysis are valuable information that may be used to optimize the modalities and parameters for lamellar tissue processing. The UHR-OCT is a powerful approach that will allow us to further evaluate the tissue response to different processing techniques for posterior lamellar keratoplasty. It may also provide information that can be used to correlate with postoperative clinical outcomes. UHR-OCT has the potential to become a routine part of tissue

Compatibilization of low-density polyethylene/polystyrene blends by segmented EB(PS-block-EB)(n) block copolymers

NARCIS (Netherlands)

Kroeze, E; ten Brinke, G.; Hadziioannou, G

Hydrogenated segmented poly[butadiene-block-(styrene-block-butadiene)(n)] block copolymers, which were developed by use of a polymeric iniferter technique, were tested on their compatibilizing effectiveness for (10/90) LDPE/PS blends. They were found to be effective compatibilizers for this mixture,

Novel in situ coordinated cerium salt/acrylonitrile-butadiene rubber composite

International Nuclear Information System (INIS)

Han, Jianjun; Lu, Haifeng; Zhang, Jie; Feng, Shengyu

2012-01-01

A novel rubber composite of acrylonitrile-butadiene rubber (NBR) filled with cerium salt particles was vulcanized via in situ coordination for the first time. The resulting materials exhibit good mechanical properties. Curing characteristics analysis, differential scanning calorimetry, X-ray photoelectron spectroscopy, tensile testing, and an equilibrium swelling method were used for the characterization of the composite. The results in this paper indicate that the composite is a kind of elastomer based on the in situ coordination crosslinking interactions between the nitrile groups (–CN) of NBR and cerium ions. The mechanical properties of vulcanized cerium salt/ NBR rubber are altered when changing the sorts of cerium salt. Moreover, these materials show good irradiation resistance because of the introduction of the cerium salt. -- Highlights: ► Cerium salts were firstly used to vulcanize the acrylonitrile-butadiene rubber. ► Cerium salts act as not only crosslink agents but also reinforcing fillers in the matrix. ► These materials show good irradiation resistance and mechanical properties at same time.

Effect of molecular weight distribution on e-beam exposure properties of polystyrene

International Nuclear Information System (INIS)

Dey, Ripon Kumar; Cui Bo

2013-01-01

Polystyrene is a negative electron beam resist whose exposure properties can be tuned simply by using different molecular weights (Mw). Most previous studies have used monodisperse polystyrene with a polydispersity index (PDI) of less than 1.1 in order to avoid any uncertainties. Here we show that despite the fact that polystyrene’s sensitivity is inversely proportional to its Mw, no noticeable effect of very broad molecular weight distribution on sensitivity, contrast and achievable resolution is observed. It is thus unnecessary to use the costly monodisperse polystyrene for electron beam lithography. Since the polydispersity is unknown for general purpose polystyrene, we simulated a high PDI polystyrene by mixing in a 1:1 weight ratio two polystyrene samples with Mw of 170 and 900 kg mol −1 for the high Mw range, and 2.5 and 13 kg mol −1 for the low Mw range. The exposure property of the mixture resembles that of a monodisperse polystyrene with similar number averaged molecular weight (Mn)-bar, which indicates that it is (Mn)-bar rather than (Mw)-bar (weight averaged molecular weight) that dominates the exposure properties of polystyrene resist. This also implies that polystyrene of a certain molecular weight can be simulated by a mixture of two polystyrenes having different molecular weights. (paper)

Effect of planar extension on the structure and mechanical properties of polystyrene-poly(ethylene-¤co¤-butylene)-polystyrene triblock copolymers

DEFF Research Database (Denmark)

Daniel, C.; Hamley, I.W.; Mortensen, K.

2000-01-01

Two thermoplastic poly(styrene)-poly(ethylene-co-butylene) -poly(styrene) triblock copolymers containing either spherical or cylindrical poly(styrene) microdomains were pre-oriented through extensional flow. Small angle neutron scattering (SANS) measurements revealed that the pre-oriented triblock...

A rheo-optical apparatus for real time kinetic studies on shear-induced alignment of self-assembled soft matter with small sample volumes

Science.gov (United States)

Laiho, Ari; Ikkala, Olli

2007-01-01

In soft materials, self-assembled nanoscale structures can allow new functionalities but a general problem is to align such local structures aiming at monodomain overall order. In order to achieve shear alignment in a controlled manner, a novel type of rheo-optical apparatus has here been developed that allows small sample volumes and in situ monitoring of the alignment process during the shear. Both the amplitude and orientation angles of low level linear birefringence and dichroism are measured while the sample is subjected to large amplitude oscillatory shear flow. The apparatus is based on a commercial rheometer where we have constructed a flow cell that consists of two quartz teeth. The lower tooth can be set in oscillatory motion whereas the upper one is connected to the force transducers of the rheometer. A custom made cylindrical oven allows the operation of the flow cell at elevated temperatures up to 200 °C. Only a small sample volume is needed (from 9 to 25 mm3), which makes the apparatus suitable especially for studying new materials which are usually obtainable only in small quantities. Using this apparatus the flow alignment kinetics of a lamellar polystyrene-b-polyisoprene diblock copolymer is studied during shear under two different conditions which lead to parallel and perpendicular alignment of the lamellae. The open device geometry allows even combined optical/x-ray in situ characterization of the alignment process by combining small-angle x-ray scattering using concepts shown by Polushkin et al. [Macromolecules 36, 1421 (2003)].

Synthesis in pilot plant scale and physical properties of sulfonated polystyrene

Directory of Open Access Journals (Sweden)

Martins Cristiane R.

2003-01-01

Full Text Available The homogenous sulfonation of polystyrene was developed in a pilot plant scale producing polymers with different sulfonation degrees (18 to 22 mole % of sulfonated styrene units. The reaction yield depends chiefly on the concentration ratio of acetyl sulfate and polystyrene. The morphological and thermal properties of the sulfonated polystyrene obtained by homogeneous sulfonation were studied by means of scanning electron microscopy, differential scanning calorimetry and thermogravimetry. The glass transition temperature of sulfonated polystyrene increases in relation to pure polystyrene and DCp was evaluated in order to confirm the strong interactions among the ~SO3H groups.

Micellar Structures of Hydrophilic/Lipophilic and Hydrophilic/Fluorophilic Poly(2-oxazoline) Diblock Copolymers in Water

DEFF Research Database (Denmark)

Ivanova, Ruzha; Komenda, Thomas; Bonné, Tune B.

2008-01-01

Amphiphilic poly(2-alkyl-2-oxazoline) diblock copolymers of 2-methyl-2-oxazoline (MOx) building the hydrophilic block and either 2-nonyl-2-oxazoline (NOx) for the hydrophobic or 2-(1H,1H',2H,2H'-perfluorohexyl)-2-oxazoline (FOx) for the fluorophilic block were synthesized by sequential living...

Mechanical and Thermal Properties of Styrene Butadiene Rubber - Functionalized Carbon Nanotubes Nanocomposites

KAUST Repository

Laoui, Tahar

2013-01-01

The effect of reinforcing styrene butadiene rubber (SBR) with functionalized carbon nanotubes on the mechanical and thermal properties of the nanocomposite was investigated. Multi-walled carbon nanotubes (CNTs) were functionalized with phenol

ESR studies of the radiation effects on polystyrene

International Nuclear Information System (INIS)

Garrett, R.W.; O'Donnell, J.H.; Pomery, P.J.

1976-01-01

The aim of this work was to investigate the polystyrene system (both pure and commercial samples) to elucidate the type and percentage of each paramagnetic species upon exposure to various irradiation doses. The size of dose plays a vital role in the type of spectra obtained. Upon irradiation in vacuo, polystyrene displays ESR spectra which are basically triplet in character but the line spacing and intensities of components are observed to depend on the magnitude of the irradiation dose. G value for the total radicals present and for the individual species present as a function of dose have been obtained. The relative concentration of each paramagnetic species has been determined through computer simulation of the observed ESR spectra. The relative stability of the different species with respect to temperature is discussed. The results for deuterated polystyrene is used to support those obtained for the unsubstituted polystyrene system. (author)

Constancy in composition of polystyrene and polymethylmethacrylate plastics

International Nuclear Information System (INIS)

Schulz, R.J.; Nath, R.

1979-01-01

Variations in the atomic compostion, and mass and electron densities of polystyrene and polymethylmethacrylate (PMM) plastics were assessed from experimentally determined mass attenuation coefficients for 125 I and 137 Cs gamma rays. The means and standard deviations in the mass densities of 16 samples of PMM and 10 samples of polystyrene were found to be 1.174 +- 1.4% and 1.042 +- 0.6% g/cm 3 , respectively. Based upon transmission measurements on various solutions of ethyl alcohol in water, the standard deviations in the effective atomic numbers of PMM and polystyrene were determined to be 0.77% and 1.3%, respectively. Based upon experimentally determined mass attenuation coefficients for 137 Cs, the standard deviations in electron density for PMM and polystyrene were 0.5% and 1.2%, respectively. Similar measurements on tap water and two grades of distilled water failed to detect any differences in atomic composition

Structuring of Interface-Modified Polymer Blends

DEFF Research Database (Denmark)

Lyngaae-Jørgensen, Jørgen

1999-01-01

The paper treats the case where blends of polystyrene (PS), poly (dimethylsiloxane) (PDMS) and a diblock copolymer of PS and PDMS are used as model materials. This modelsystem is predicted to be "stable" in discrete blends in simple shear flow. Stable in the sence that the block copolymer can not...

Intradomain phase transitions in flexible block copolymers with self-aligning segments

Science.gov (United States)

Burke, Christopher J.; Grason, Gregory M.

2018-05-01

We study a model of flexible block copolymers (BCPs) in which there is an enlthalpic preference for orientational order, or local alignment, among like-block segments. We describe a generalization of the self-consistent field theory of flexible BCPs to include inter-segment orientational interactions via a Landau-de Gennes free energy associated with a polar or nematic order parameter for segments of one component of a diblock copolymer. We study the equilibrium states of this model numerically, using a pseudo-spectral approach to solve for chain conformation statistics in the presence of a self-consistent torque generated by inter-segment alignment forces. Applying this theory to the structure of lamellar domains composed of symmetric diblocks possessing a single block of "self-aligning" polar segments, we show the emergence of spatially complex segment order parameters (segment director fields) within a given lamellar domain. Because BCP phase separation gives rise to spatially inhomogeneous orientation order of segments even in the absence of explicit intra-segment aligning forces, the director fields of BCPs, as well as thermodynamics of lamellar domain formation, exhibit a highly non-linear dependence on both the inter-block segregation (χN) and the enthalpy of alignment (ɛ). Specifically, we predict the stability of new phases of lamellar order in which distinct regions of alignment coexist within the single mesodomain and spontaneously break the symmetries of the lamella (or smectic) pattern of composition in the melt via in-plane tilt of the director in the centers of the like-composition domains. We further show that, in analogy to Freedericksz transition confined nematics, the elastic costs to reorient segments within the domain, as described by the Frank elasticity of the director, increase the threshold value ɛ needed to induce this intra-domain phase transition.

Elongational viscosity of monodisperse and bidisperse polystyrene melts

DEFF Research Database (Denmark)

Nielsen, Jens Kromann; Rasmussen, Henrik K.; Hassager, Ole

2006-01-01

The start-up and steady uniaxial elongational viscosity have been measured for two monodisperse polystyrene melts with molecular weights of 52 and 103 kg/mole, and for three bidisperse polystyrene melts. The monodisperse melts show a maximum in the steady elongational viscosity vs. the elongational...

Macromolecular Colloids of Diblock Poly(amino acids) That Bind Insulin.

Science.gov (United States)

Constancis; Meyrueix; Bryson; Huille; Grosselin; Gulik-Krzywicki; Soula

1999-09-15

The diblock polymer poly(l-leucine-block-l-glutamate), bLE, was synthesized by acid hydrolysis of the ester poly(l-leucine-block-l-methyl glutamate). During the hydrolysis reaction the leucine block precipitates from the reaction mixture, forming nanosized particulate structures. These particles can be purified and further suspended in water or in 0.15 M phosphate saline buffer (PBS) to give stable, colloidal dispersions. TEM analysis shows the predominant particle form to be that of platelets with a diameter of 200 nm. Smaller cylindrical or spherical particles form a relatively minor fraction of the sample. After fractionation, analysis shows the platelets to be compositionally rich in leucine, while the spheres are glutamate-rich. (1)H NMR, CD, and X-ray diffraction indicate that the core of the platelets is composed of crystalline, helical leucine segments. The poly(l-glutamate) polyelectrolyte brush extending out from the two faces of the disk stabilizes individual particles from flocculation. At pH 7.4, the nanoparticles (platelets and cylinders) spontaneously adsorb proteins, such as insulin, directly from solution. Partial desorption of the protein in its native configuration can be induced by simple dilution. The reversibility of the insulin-nanoparticle complex is the basis for a potential new delivery system. Copyright 1999 Academic Press.

Enhancing mechanical and thermal properties of styrene-butadiene rubber/carboxylated acrylonitrile butadiene rubber blend by the usage of graphene oxide with diverse oxidation degrees

Science.gov (United States)

Xue, Xiaodong; Yin, Qing; Jia, Hongbing; Zhang, Xuming; Wen, Yanwei; Ji, Qingmin; Xu, Zhaodong

2017-11-01

Graphene oxide (GO) with various oxidation degrees were prepared through a modified Hummer's method by varying the dosage of oxidizing agent. Styrene-butadiene rubber (SBR)/carboxylated acrylonitrile butadiene rubber (XNBR)/GO nanocomposites were fabricated by aqueous-phase mixing of GO colloidal dispersion with SBR latex and a small loading of XNBR latex, followed by co-coagulation. Effects of GO oxidation degree on the morphology, structure, mechanical and thermal properties of nanocomposites were thoroughly investigated. The results showed that the mechanical strength of nanocomposites were enhanced with the increase of oxidation degree of GO. Especially, when the weight ratio of KMnO4 to graphite was 15/5, the tensile strength, tear strength and thermal conductivity of SBR/XNBR/GO filled with 3 phr (parts per hundred rubber) GO increased by 255.3%, 141.5% and 22.8%, respectively, compared to those of neat SBR/XNBR blend. In addition, the thermal stability and the solvent resistance of the nanocomposites were also improved significantly. This work suggested that GO with higher oxidation degree could effectively improve the properties of SBR/XNBR blend.

Dynamic swelling of tunable full-color block copolymer photonic gels via counterion exchange.

Science.gov (United States)

Lim, Ho Sun; Lee, Jae-Hwang; Walish, Joseph J; Thomas, Edwin L

2012-10-23

One-dimensionally periodic block copolymer photonic lamellar gels with full-color tunability as a result of a direct exchange of counteranions were fabricated via a two-step procedure comprising the self-assembly of a hydrophobic block-hydrophilic polyelectrolyte block copolymer, polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP), followed by sequential quaternization of the P2VP layers in 1-bromoethane solution. Depending on the hydration characteristics of each counteranion, the selective swelling of the block copolymer lamellar structures leads to large tunability of the photonic stop band from blue to red wavelengths. More extensive quaternization of the P2VP block allows the photonic lamellar gels to swell more and red shift to longer wavelength. Here, we investigate the dynamic swelling behavior in the photonic gel films through time-resolved in situ measurement of UV-vis transmission. We model the swelling behavior using the transfer matrix method based on the experimentally observed reflectivity data with substitution of appropriate counterions. These tunable structural color materials may be attractive for numerous applications such as high-contrast displays without using a backlight, color filters, and optical mirrors for flexible lasing.

Thermoresponsive Self-Assembly of Nanostructures from a Collagen-Like Peptide-Containing Diblock Copolymera

OpenAIRE

Luo, Tianzhi; He, Lirong; Theato, Patrick; Kiick, Kristi L.

2014-01-01

Temperature-triggered formation of nanostructures with distinct biological activity offers opportunities in selective modification of matrices and in drug delivery. Toward these ends, diblock polymers comprising poly(diethylene glycol methyl ether methacrylate) (PDEGMEMA) conjugated to a triple helix-forming collagen-like peptide (CLP) is produced. The ability of the CLP domain to maintain its triple helix conformation after conjugation with the polymer is confirmed via circular dichroism (CD...

Lipase polystyrene giant amphiphiles.

Science.gov (United States)

Velonia, Kelly; Rowan, Alan E; Nolte, Roeland J M

2002-04-24

A new type of giant amphiphilic molecule has been synthesized by covalently connecting a lipase enzyme headgroup to a maleimide-functionalized polystyrene tail (40 repeat units). The resulting biohybrid forms catalytic micellar rods in water.

Chain conformations of the component polymers and the microphase separation structures of homopolymer/block coplymer blends

International Nuclear Information System (INIS)

Torikai, Naoya; Mogi, Yasuhiro; Matsushita, Yushu; Noda, Ichiro; Han, C.C.

1993-01-01

Microdomain spacings of lamellar structures formed by styrene homopolymer/styrene-2-vinylpyridine diblock copolymer/2-vinylpyridine homopolymer blends were measured by small-angle X-ray scattering (SAXS) and single chain conformations of block copolymers in the same blend system were measured by small-angle neutron scattering (SANS). The molecular weight of diblock copolymers is 78K-72K, and three kinds of styrene homopolymer (S H ) and 2-vinylpyridine homopolymer (P H ) pairs were blended, their molecular weight ratios to that of host block chains were 0.17, 0.38, and 0.78, respectively. Two blend ratios of homopolymer (H)/block copolymer (B), i.e. 1/2 and 1/1 were examined. It was found that the domain spacings of all blends are larger than that of pure block copolymer and that they are increasing with increasing the molecular weight of homopolymers and/or with increasing the volume fraction of homopolymers. Further, block chains in the blends were confirmed to have almost the same chain dimension as that of block chain in pure block copolymer system in the direction parallel to the domain interface irrespective of molecular weight and volume fraction of homopolymers. (author)

pH Memory Effects of Tunable Block Copolymer Photonic Gels and Their Applications

Science.gov (United States)

Kang, Youngjong; Thomas, Edwin L.

2007-03-01

Materials with hysteresis, showing a bistable state to the external stimuli, have been widely investigated due to their potential applications. For example, they could be used as memory devices or optical switches when they have magnetic or optical hysteresis response to the external stimuli. Here we report pH tunable photonic gels which are spontaneously assembled from block copolymers. The general idea of this research is based on the selective swelling of block copolymer lamellar mesogels, where the solubility of one block is responsive to the change of pH. In this system, the domain spacing of the lamellar is varied with the extent of swelling. As a model system, we used protonated polystyrene-b-poly(2-vinly pyridine) (PS-b-P2VP) block copolymers forming lamellar structures. The photonic gel films prepared from protonated PS-b-P2VP show a strong reflectance in aqueous solution and the band position was varied with pH. Interestingly, a very strong optical hysteresis was observed while the reflection band of photonic gels was tuned by changing pH. We anticipate that pH tunable photonic gels with hysteresis can be applicable to novel applications such as a component of memory devices, photonic switches or drug delivery vehicles.

Hierarchical self-assembly of two-length-scale multiblock copolymers

International Nuclear Information System (INIS)

Brinke, Gerrit ten; Loos, Katja; Vukovic, Ivana; Du Sart, Gerrit Gobius

2011-01-01

The self-assembly in diblock copolymer-based supramolecules, obtained by hydrogen bonding short side chains to one of the blocks, as well as in two-length-scale linear terpolymers results in hierarchical structure formation. The orientation of the different domains, e.g. layers in the case of a lamellar-in-lamellar structure, is determined by the molecular architecture, graft-like versus linear, and the relative magnitude of the interactions involved. In both cases parallel and perpendicular arrangements have been observed. The comb-shaped supramolecules approach is ideally suited for the preparation of nanoporous structures. A bicontinuous morphology with the supramolecular comb block forming the channels was finally achieved by extending the original approach to suitable triblock copolymer-based supramolecules.

Polystyrene Microbeads by Dispersion Polymerization: Effect of Solvent on Particle Morphology

Directory of Open Access Journals (Sweden)

Lei Jinhua

2014-01-01

Full Text Available Polystyrene microspheres (PS were synthesized by dispersion polymerization in ethanol/2-Methoxyethanol (EtOH/EGME blend solvent using styrene (St as monomer, azobisisobutyronitrile (AIBN as initiator, and PVP (polyvinylpyrrolidone K-30 as stabilizer. The typical recipe of dispersion polymerization is as follows: St/Solvent/AIBN/PVP = 10 g/88 g/0.1 g/2 g. The morphology of polystyrene microspheres was characterized by the scanning electron microscopy (SEM and the molecular weights of PS particles were measured by the Ubbelohde viscometer method. The effect of ethanol content in the blend solvent on the morphology and molecular weight of polystyrene was studied. We found that the size of polystyrene microspheres increased and the molecular weight of polystyrene microspheres decreased with the decreasing of the ethanol content in the blend solvent from 100 wt% to 0 wt%. What is more, the size monodispersity of polystyrene microspheres was quite good when the pure ethanol or pure 2-Methoxyethanol was used; however when the blend ethanol/2-Methoxyethanol solvent was used, the polystyrene microspheres became polydisperse. We further found that the monodispersity of polystyrene microspheres can be significantly improved by adding a small amount of water into the blend solvent; the particles became monodisperse when the content of water in the blend solvent was up to 2 wt%.

Effect of hydrogenation disproportionation conditions on magnetic anisotropy in Nd-Fe-B powder prepared by dynamic hydrogenation disproportionation desorption recombination

Directory of Open Access Journals (Sweden)

Masao Yamazaki

2017-05-01

Full Text Available Various anisotropic Nd-Fe-B magnetic powders were prepared by the dynamic hydrogenation disproportionation desorption recombination (d-HDDR treatment with different hydrogenation disproportionation (HD times (tHD. The resulting magnetic properties and microstructural changes were investigated. The magnetic anisotropy was decreased with increasing tHD. In the d-HDDR powders with higher magnetic anisotropy, fine (200–600 nm and coarse (600–1200 nm Nd2Fe14B grains were observed. The coarse Nd2Fe14B grains showed highly crystallographic alignment of the c-axis than fine Nd2Fe14B grains. In the highly anisotropic Nd2Fe14B d-HDDR powder, a large area fraction of lamellar-like structures consisting of NdH2 and α-Fe were observed after HD treatment. Furthermore, the mean diameter of the lamellar-like regions, where lamellar-like structures orientate to the same direction in the HD-treated alloys was close to that of coarse Nd2Fe14B grains after d-HDDR treatment. Thus, the lamellar-like regions were converted into the crystallographically aligned coarse Nd2Fe14B grains during desorption recombination treatment, and magnetic anisotropy is closely related to the volume fraction of lamellar-like regions observed after HD treatment.

An atomic force microscopy study on the transition from mushrooms to octopus surface ''micelles'' by changing the solvent quality

NARCIS (Netherlands)

Stamouli, A.; Pelletier, E.; Koutsos, V; van der Vegte, E.W.; Hadziioannou, G

1996-01-01

Atomic force microscopy (AFM) is used to study the behavior of a diblock copolymer onto a solid surface while the solvent quality is changed. In a first step, the copolymer poly(2-vinylpyridine)/polystyrene (P2VP/PS) is adsorbed onto mica from a selective solvent (the PS block is well solvated and

The impact of fluorescent dyes on the performances of polystyrene-based plastic scintillators

International Nuclear Information System (INIS)

Zhu, Jun; Deng, Cheng; Jiang, Huimin; Zheng, Zhanlong; Gong, Rui; Bi, Yutie; Zhang, Lin; Lin, Runxiong

2016-01-01

To investigate the influence of both the first luminescent additive and the wavelength-shifter on the performance of plastic scintillator, a series of polystyrene-based scintillator had been prepared by thermal polymerization. Three first luminescent additives (PPO, p-TP and b-PBD) and four wavelength-shifters (POPOP, Bis-MSB, Me-MSB and DPA) were added to the scintillators respectively. The comparison results showed that PPO and POPOP were the most adequate fluorescent dyes for the polystyrene-based plastic scintillator. Moreover, with the increase of the concentration of PPO and POPOP, the fluorescence intensity and light yield were increased firstly and then decreased. The plastic scintillator containing 2% PPO and 0.02% POPOP had the highest fluorescence intensity and light yield.

The impact of fluorescent dyes on the performances of polystyrene-based plastic scintillators

Energy Technology Data Exchange (ETDEWEB)

Zhu, Jun [Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Engineering Research Center of High Performance Polymer and Molding Technology, Ministry of Education, Qingdao University of Science and Technology, Qingdao 266042 (China); Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621010 (China); Deng, Cheng; Jiang, Huimin [Engineering Research Center of High Performance Polymer and Molding Technology, Ministry of Education, Qingdao University of Science and Technology, Qingdao 266042 (China); Zheng, Zhanlong; Gong, Rui [Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621010 (China); Bi, Yutie [Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621010 (China); Zhang, Lin, E-mail: zhlmy@sina.com [Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Lin, Runxiong, E-mail: qdlrx@qust.edu.cn [Engineering Research Center of High Performance Polymer and Molding Technology, Ministry of Education, Qingdao University of Science and Technology, Qingdao 266042 (China)

2016-11-01

To investigate the influence of both the first luminescent additive and the wavelength-shifter on the performance of plastic scintillator, a series of polystyrene-based scintillator had been prepared by thermal polymerization. Three first luminescent additives (PPO, p-TP and b-PBD) and four wavelength-shifters (POPOP, Bis-MSB, Me-MSB and DPA) were added to the scintillators respectively. The comparison results showed that PPO and POPOP were the most adequate fluorescent dyes for the polystyrene-based plastic scintillator. Moreover, with the increase of the concentration of PPO and POPOP, the fluorescence intensity and light yield were increased firstly and then decreased. The plastic scintillator containing 2% PPO and 0.02% POPOP had the highest fluorescence intensity and light yield.

Hybrid Technique of Lamellar Keratoplasty (DMEK-S

Directory of Open Access Journals (Sweden)

Pavel Studeny

2013-01-01

Full Text Available Purpose: To evaluate the outcomes of the hybrid technique of posterior lamellar keratoplasty (DMEK-S. Materials and Methods: 71 eyes of 55 patients enrolled in a single-center study underwent posterior lamellar keratoplasty with a hybrid lamella DMEK-S implanted using a solution implantation technique, owing to endothelial dysfunction. The outcome measures studied were visual acuity and endothelial cell density. Results: The rate of endothelial cell loss caused by surgery was 43.8%. During followups, we observed the stabilization of postoperative findings, or at minimum a very low rate of corneal endothelial cell loss. The UCDVA and BCDVA dramatically improved postoperatively. The rebubbling rate in our group of patients was 61.9%. We replaced the lamella due to its failure or malfunction in 17 patients (23.9%. Conclusion: In summary, DMEK-S combines the advantages of DSEK/DSAEK and DMEK. The central zone of bare Descemet’s membrane and endothelium allows for very good visual outcomes, and the peripheral rim allows for better manipulation of the lamella during implantation. It is an effective method of treating the endothelial dysfunction of various etiologies, but the high complication rate needs to be addressed before widespread implementation of the technique in the future.

Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces.

Science.gov (United States)

Zou, Shan; Hong, Rui; Emrick, Todd; Walker, Gilbert C

2007-02-13

Hierarchical, high-density, ordered patterns were fabricated on Si substrates by self-assembly of CdSe nanoparticles within approximately 20-nm-thick diblock copolymer films in a controlled manner. Surface-modified CdSe nanoparticles formed well-defined structures within microphase-separated polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) domains. Trioctylphosphine oxide (TOPO)-coated CdSe nanoparticles were incorporated into PS domains and polyethylene glycol-coated CdSe nanoparticles were located primarily in the P2VP domains. Nearly close-packed CdSe nanoparticles were clearly identified within the highly ordered patterns on Si substrates by scanning electron microscopy (SEM). Contact angle measurements together with SEM results indicate that TOPO-CdSe nanoparticles were partially placed at the air/copolymer interface.

Modification of Jute Fibers with Polystyrene via Atom Transfer Radical Polymerization

DEFF Research Database (Denmark)

Plackett, David; Jankova, Katja Atanassova; Egsgaard, Helge

2005-01-01

Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified...... to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite...

Novel in situ coordinated cerium salt/acrylonitrile-butadiene rubber composite

Energy Technology Data Exchange (ETDEWEB)

Han, Jianjun [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Lu, Haifeng, E-mail: lhf@sdu.edu.cn [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Zhang, Jie [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Feng, Shengyu, E-mail: fsy@sdu.edu.cn [Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China)

2012-09-14

A novel rubber composite of acrylonitrile-butadiene rubber (NBR) filled with cerium salt particles was vulcanized via in situ coordination for the first time. The resulting materials exhibit good mechanical properties. Curing characteristics analysis, differential scanning calorimetry, X-ray photoelectron spectroscopy, tensile testing, and an equilibrium swelling method were used for the characterization of the composite. The results in this paper indicate that the composite is a kind of elastomer based on the in situ coordination crosslinking interactions between the nitrile groups (-CN) of NBR and cerium ions. The mechanical properties of vulcanized cerium salt/ NBR rubber are altered when changing the sorts of cerium salt. Moreover, these materials show good irradiation resistance because of the introduction of the cerium salt. -- Highlights: Black-Right-Pointing-Pointer Cerium salts were firstly used to vulcanize the acrylonitrile-butadiene rubber. Black-Right-Pointing-Pointer Cerium salts act as not only crosslink agents but also reinforcing fillers in the matrix. Black-Right-Pointing-Pointer These materials show good irradiation resistance and mechanical properties at same time.

Comparative characteristics of polystyrene scintillation strips

International Nuclear Information System (INIS)

Gapienko, V.A.; Denisov, A.G.; Mel'nikov, E.A.

1992-01-01

Results are provided for a study of the main characteristics of polystyrene scintillation strips with a cross-section of 200 x 10 mm with two different scintillation-additive compositions: 1.5% p-terphenyl + 0.01% POPOP and 1.5% p-terphenyl + 0.01% DBP. The mean light-attenuation lengths are 180 cm and 260 cm, respectively, for strips with POPOP and DBP. The emittances of the polystyrene scintillators with DBP and POPOP additives have a ratio of 0.8:1.0 as recorded by an FEU-110 photomultiplier. 2 refs., 1 fig., 2 tabs

Local Segmental Dynamics and Stresses in Polystyrene - C$_{60}$ Mixtures

OpenAIRE

Vogiatzis, Georgios G.; Theodorou, Doros N.

2014-01-01

The polymer dynamics of homogeneous C$_{60}$-polystyrene mixtures in the molten state are studied via molecular simulations using two interconnected levels of representation for polystyrene nanocomposites: (a) A coarse-grained representation, in which each polystyrene repeat unit is mapped into a single "superatom" and each fullerene is viewed as a spherical shell. Equilibration of coarse-grained polymer-nanoparticle systems at all length scales is achieved via connectivity-altering Monte Car...

Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT).

Science.gov (United States)

Kaiser, Andreas; Brandau, Sven; Klimpel, Michael; Barner-Kowollik, Christopher

2010-09-15

In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, $\\overline M _{\\rm n} $, of the NBR can be varied between a few thousand and 60 000 g · mol(-1) with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization-mass spectrometry (ESI-MS). Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast and robust method for the determination of microstructure and composition in butadiene, styrene-butadiene, and isoprene rubber by near-infrared spectroscopy.

Science.gov (United States)

Vilmin, Franck; Dussap, Claude; Coste, Nathalie

2006-06-01

In the tire industry, synthetic styrene-butadiene rubber (SBR), butadiene rubber (BR), and isoprene rubber (IR) elastomers are essential for conferring to the product its properties of grip and rolling resistance. Their physical properties depend on their chemical composition, i. e., their microstructure and styrene content, which must be accurately controlled. This paper describes a fast, robust, and highly reproducible near-infrared analytical method for the quantitative determination of the microstructure and styrene content. The quantitative models are calculated with the help of pure spectral profiles estimated from a partial least squares (PLS) regression, using (13)C nuclear magnetic resonance (NMR) as the reference method. This versatile approach allows the models to be applied over a large range of compositions, from a single BR to an SBR-IR blend. The resulting quantitative predictions are independent of the sample path length. As a consequence, the sample preparation is solvent free and simplified with a very fast (five minutes) hot filming step of a bulk polymer piece. No precise thickness control is required. Thus, the operator effect becomes negligible and the method is easily transferable. The root mean square error of prediction, depending on the rubber composition, is between 0.7% and 1.3%. The reproducibility standard error is less than 0.2% in every case.

Chain conformations of ABA triblock coplymers in microphase-separated structures for SANS

International Nuclear Information System (INIS)

Matsushita, Y.; Nomura, M.; Watanabe, J.; Mogi, Y.; Noda, I.; Han, C.C.

1993-01-01

Single chain conformations of center block, polystyrene, of poly(2-vinylpyridine-b-styrene-b-2-vinylpyridine)(PSP) triblock copolymers of the ABA type in bulk were measured by small angle neutron scattering (SANS), while microphase separation structures were studied by small angle X-ray Scattering (SAXS) and transmission electron microscopy (TEM). From the morphological observations, PSP block copolymers have confirmed to have alternating lamellar structure both when φs = 0.33 and φs = 0.5, where φs is the volume fraction of polystyrene blocks. It was also clarified that the chain dimension of center blocks of sample with φs = 0.33 is smaller than that of sample with φs = 0.5. This result may mean that the center blocks have bridge-righ conformation when φs = 0.33 while they have loop-rich conformation when φs = 0.5. (author)

Modeling of continuous free-radical butadiene-styrene copolymerization process by the Monte Carlo method

Directory of Open Access Journals (Sweden)

T. A. Mikhailova

2016-01-01

Full Text Available In the paper the algorithm of modeling of continuous low-temperature free-radical butadiene-styrene copolymerization process in emulsion based on the Monte-Carlo method is offered. This process is the cornerstone of industrial production butadiene – styrene synthetic rubber which is the most widespread large-capacity rubber of general purpose. Imitation of growth of each macromolecule of the formed copolymer and tracking of the processes happening to it is the basis of algorithm of modeling. Modeling is carried out taking into account residence-time distribution of particles in system that gives the chance to research the process proceeding in the battery of consistently connected polymerization reactors. At the same time each polymerization reactor represents the continuous stirred tank reactor. Since the process is continuous, it is considered continuous addition of portions to the reaction mixture in the first reactor of battery. The constructed model allows to research molecular-weight and viscous characteristics of the formed copolymerization product, to predict the mass content of butadiene and styrene in copolymer, to carry out calculation of molecular-weight distribution of the received product at any moment of conducting process. According to the results of computational experiments analyzed the influence of mode of the process of the regulator introduced during the maintaining on change of characteristics of the formed butadiene-styrene copolymer. As the considered process takes place with participation of monomers of two types, besides listed the model allows to research compositional heterogeneity of the received product that is to carry out calculation of composite distribution and distribution of macromolecules for the size and structure. On the basis of the proposed algorithm created the software tool that allows you to keep track of changes in the characteristics of the resulting product in the dynamics.

Recycling of engineering plastics from waste electrical and electronic equipments: influence of virgin polycarbonate and impact modifier on the final performance of blends.

Science.gov (United States)

Ramesh, V; Biswal, Manoranjan; Mohanty, Smita; Nayak, Sanjay K

2014-05-01

This study is focused on the recovery and recycling of plastics waste, primarily polycarbonate, poly(acrylonitrile-butadiene-styrene) and high impact polystyrene, from end-of-life waste electrical and electronic equipments. Recycling of used polycarbonate, acrylonitrile-butadiene-styrene, polycarbonate/acrylonitrile-butadiene-styrene and acrylonitrile-butadiene-styrene/high impact polystrene material was carried out using material recycling through a melt blending process. An optimized blend composition was formulated to achieve desired properties from different plastics present in the waste electrical and electronic equipments. The toughness of blended plastics was improved with the addition of 10 wt% of virgin polycarbonate and impact modifier (ethylene-acrylic ester-glycidyl methacrylate). The mechanical, thermal, dynamic-mechanical and morphological properties of recycled blend were investigated. Improved properties of blended plastics indicate better miscibility in the presence of a compatibilizer suitable for high-end application.

Minimal compliance design for metal–ceramic composites with lamellar microstructures

DEFF Research Database (Denmark)

Piat, R.; Sinchuk, Y.; Vasoya, M.

2011-01-01

of lamellar domains. With local ceramic volume fraction and lamella orientation chosen as the design variables, a minimum compliance optimization problem is solved based on topology optimization and finite element methods for metal–ceramic samples with different geometries and boundary conditions...

One-step exfoliation and surface modification of lamellar hydroxyapatite by intercalation of glucosamine

Energy Technology Data Exchange (ETDEWEB)

Luo, Honglin [Research Institute for Biomaterials and Transportation, East China Jiaotong University, Nanchang, 330013 (China); School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Li, Wei; Ji, Dehui [Research Institute for Biomaterials and Transportation, East China Jiaotong University, Nanchang, 330013 (China); Zuo, Guifu [Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, Hebei United University, Tangshan, 063009 (China); Xiong, Guangyao, E-mail: xiongguangyao@163.com [Research Institute for Biomaterials and Transportation, East China Jiaotong University, Nanchang, 330013 (China); Zhu, Yong [School of Chemical Engineering, Tianjin University, Tianjin, 300072 (China); Li, Lili; Han, Ming [Research Institute for Biomaterials and Transportation, East China Jiaotong University, Nanchang, 330013 (China); Wu, Caoqun [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Wan, Yizao, E-mail: yzwantju@126.com [Research Institute for Biomaterials and Transportation, East China Jiaotong University, Nanchang, 330013 (China); School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China)

2016-04-15

Effective exfoliation is crucial to the application of layered materials in many fields. Herein, we report a novel effective, scalable, and ecofriendly method for the exfoliation of lamellar HAp by glucosamine intercalation such that individual HAp nanoplates can be obtained. The as-exfoliated HAp nanoplates were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric (TG) analysis. It is found that the glucosamine intercalation not only results in complete exfoliation of lamellar HAp but also introduces the glucosamine molecules onto the surface of individual HAp nanoplates, thus obtaining separated glucosamine-grafted HAp nanoplates (Glu-HAps). Results from MTT assay demonstrate that glucosamine grafting on HAp nanoplates greatly improves the cell growth and proliferation as compared to nongrafted HAp counterparts. - Highlights: • Glucosamine was used as intercalation agent to exfoliate lamellar hydroxyapatite. • Glucosamine was grafted onto the as-exfoliated nanoplate-like hydroxyapatite. • Exfoliation and surface grafting were accomplished in one step. • Glucosamine-grafted HAp showed improved biocompatibility over nongrafted one.

21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

Science.gov (United States)

2010-04-01

... parts by weight of a grafted rubber consisting of (i) 8-12 parts of butadiene/styrene elastomer... limitations are determined by an infrared spectro-photo-metric method titled “Infrared Spectro-photo-metric...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Heavy metal ion uptake properties of polystyrene-supported chelating polymer resins ... Synthesis, spectral characterization and redox properties of iron (II) complexes of ... Lamellar multilayer hexadecylaniline-modified gold nanoparticle films ...

Shear-induced morphology transition and microphase separation in a lamellar phase doped with clay particles.

Science.gov (United States)

Nettesheim, Florian; Grillo, Isabelle; Lindner, Peter; Richtering, Walter

2004-05-11

We report on the influence of shear on a nonionic lamellar phase of tetraethyleneglycol monododecyl ether (C12E4) in D2O containing clay particles (Laponite RD). The system was studied by means of small-angle light scattering (SALS) and small-angle neutron scattering (SANS) under shear. The SANS experiments were conducted using a H2O/D2O mixture of the respective scattering length density to selectively match the clay scattering. The rheological properties show the familiar shear thickening regime associated with the formation of multilamellar vesicles (MLVs) and a shear thinning regime at higher stresses. The variation of viscosity is less pronounced as commonly observed. In the shear thinning regime, depolarized SALS reveals an unexpectedly strong variation of the MLV size. SANS experiments using the samples with lamellar contrast reveal a change in interlamellar spacing of up to 30% at stresses that lead to MLV formation. This change is much more pronounced than the change observed, when shear suppresses thermal bilayer undulations. Microphase separation occurs, and as a consequence, the lamellar spacing decreases drastically. The coincidence of the change in lamellar spacing and the onset of MLV formation is a strong indication for a morphology-driven microphase separation.

Two types of lamellar phase in TTAB/water/pentanol system as detected by positron lifetime spectroscopy

International Nuclear Information System (INIS)

Khani, P.H.; Yadav, R.; Singh, K.C.; Jain, P.C.

2004-01-01

Positron lifetime measurements were performed in TTAB(Tetradecyl trimethyl ammonium bromide)/water/pentanol ternary systems prepared by adding varying amounts of pentanol to different mother solutions of TTAB/water system having fixed TTAB concentrations. Besides delineating various phase boundaries as obtained by other conventional techniques, positron annihilation parameters were also found to be sensitive in detecting two kinds of lamellar structures in the otherwise considered to be a single liquid crystalline D phase of the system. The existence of such lamellar structures has been demonstrated by a change in the trend of o-Ps lifetime parameter when the system passes from one type of lamellar structure to the other type. The results of such a finding are presented in this paper. (orig.)

The effectiveness of the biodegradation of raw and processed polystyrene by mealworms

Science.gov (United States)

Leluk, Karol; Hanus-Lorenz, Beata; Rybak, Justyna; Bożek, Magdalena

2017-11-01

In our studies biodegradation of four variants of polystyrene was performed. We tested: raw material (PS), processed polystyrene (PSr), building insulation material (EPS) and food packaging boxes (PSp). Materials were characterized by means melt flow ratio (MFR), shore hardness and gloss. The biochemical assessment of macromolecules (proteins, lipids and sugars) in the mealworms organisms fed with tested forms of polystyrene allowed us to set how efficient and beneficial the biodegradation of types of polystyrene is. We also evaluated the variability of bacterial community in larval guts by the use of denaturing gradient gel electrophoresis (DGGE) on the bacterial DNA of 16S rRNA genes amplified in polymerase chain reaction (PCR). The results suggest that EPS and PSp polystyrene are the most digestible for T. molitor larvae. The metabolic degradation of polystyrene is probably strictly connected with the changes in biodiversity of gut bacteria.

The effectiveness of the biodegradation of raw and processed polystyrene by mealworms

Directory of Open Access Journals (Sweden)

Leluk Karol

2017-01-01

Full Text Available In our studies biodegradation of four variants of polystyrene was performed. We tested: raw material (PS, processed polystyrene (PSr, building insulation material (EPS and food packaging boxes (PSp. Materials were characterized by means melt flow ratio (MFR, shore hardness and gloss. The biochemical assessment of macromolecules (proteins, lipids and sugars in the mealworms organisms fed with tested forms of polystyrene allowed us to set how efficient and beneficial the biodegradation of types of polystyrene is. We also evaluated the variability of bacterial community in larval guts by the use of denaturing gradient gel electrophoresis (DGGE on the bacterial DNA of 16S rRNA genes amplified in polymerase chain reaction (PCR. The results suggest that EPS and PSp polystyrene are the most digestible for T. molitor larvae. The metabolic degradation of polystyrene is probably strictly connected with the changes in biodiversity of gut bacteria.

Mortar modified with sulfonated polystyrene produced from waste plastic cups

OpenAIRE

MOTTA,L. A. C.; VIEIRA,J. G.; OMENA,T. H.; FARIA,F. A. C.; RODRIGUES FILHO,G.; ASSUNÇÃO,R. M. N.

2016-01-01

Abstract In this work, we studied the addition of sulfonated polystyrene produced from waste plastic cups as an admixture for mortars. Mortars were analyzed with polystyrene content of 0.0; 0.2; 0.6; 1.0 and 1.4% in relation to the cement mass. The influence of polystyrene on the mortars' properties was evaluated by the consistency index, water retention, water absorption, porosity, elasticity modulus, compressive strength, flexural strength, bond tensile strength and microscopy. The increase...

Field efficacy of expanded polystyrene and shredded waste polystyrene beads for mosquito control in artificial pools and field trials, Islamic Republic of Iran.

Science.gov (United States)

Soltani, A; Vatandoost, H; Jabbari, H; Mesdaghinia, A R; Mahvi, A H; Younesian, M; Hanafi-Bojd, A A; Bozorgzadeh, S

2012-10-01

Concerns about traditional chemical pesticides has led to increasing research into novel mosquito control methods. This study compared the effectiveness of 2 different types of polystyrene beads for control of mosquito larvae in south-east Islamic Republic of Iran. Simulated field trials were done in artificial pools and field trials were carried out in 2 villages in an indigenous malaria area using WHO-recommended methods. Application of expanded polystyrene beads or shredded, waste polystyrene chips to pool surfaces produced a significant difference between pre-treatment and post-treatment density of mosquitoes (86% and 78% reduction respectively 2 weeks after treatment). There was no significant difference between the efficacy of the 2 types of material. The use of polystyrene beads as a component of integrated vector management with other supportive measures could assist in the control of mosquito-borne diseases in the Islamic Republic of Iran and neighbouring countries.

Hemoglobin adducts in 1,3-butadiene exposed Czech workers: Female–male comparisons

Czech Academy of Sciences Publication Activity Database

Vacek, P. M.; Albertini, R. J.; Šrám, Radim; Upton, P.; Swenberg, J. A.

2010-01-01

Roč. 188, č. 3 (2010), s. 668-676 ISSN 0009-2797 Institutional research plan: CEZ:AV0Z50390512 Keywords : 3-Butadiene * metabolism * THB-Val hemoglobin adducts Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 2.832, year: 2010

Determining the morphology of polystyrene-block-poly(2-vinylpyridine) micellar reactors for ZnO nanoparticle synthesis.

Science.gov (United States)

El-Atwani, Osman; El-Atwani, Osman C; Aytun, Taner; Mutaf, Omer Faruk; Srot, Vesna; van Aken, Peter A; Ow-Yang, Cleva W

2010-05-18

We report the use of reverse PS-b-P2VP diblock copolymer micelles as true nanoscale-sized reactor vessels to synthesize ZnO nanoparticles. The reverse micelles were formed in toluene and then sequentially loaded with zinc acetate dihydrate and tetramethylammonium hydroxide reactants. Moreover, high spatial resolution Z-contrast imaging and EDX spectroscopy techniques were used to confirm the segregation of the Zn cation to the core of the loaded micelles. Determining the chemical distribution with high nanoscale spatial resolution is shown to complement the less direct characterization by AFM, DLS and FTIR, thus demonstrating broader implications for the characterization of hybrid nanocomposite systems.

The polymerization of aniline in polystyrene latex particles

Czech Academy of Sciences Publication Activity Database

Blinova, Natalia V.; Reynaud, S.; Roby, F.; Trchová, Miroslava; Stejskal, Jaroslav

2010-01-01

Roč. 160, 15/16 (2010), s. 1598-1602 ISSN 0379-6779 R&D Projects: GA AV ČR IAA400500905; GA ČR GA203/08/0686; GA ČR GA202/09/1626 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyaniline * polystyrene latex * polyaniline-polystyrene composite Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.871, year: 2010

Inverse cutting of posterior lamellar corneal grafts by a femtosecond laser.

Science.gov (United States)

Hjortdal, Jesper; Nielsen, Esben; Vestergaard, Anders; Søndergaard, Anders

2012-01-01

Posterior lamellar grafting of the cornea has become the preferred technique for treatment of corneal endothelial dysfunction. Posterior lamellar grafts are usually cut by a micro-keratome or a femto-second laser after the epithelial side of the donor cornea has been applanated. This approach often results in variable central graft thickness in different grafts and an increase in graft thickness towards the periphery in every graft. The purpose of this study was to evaluate if posterior lamellar grafts can be prepared from the endothelial side by a femto-second laser, resulting in reproducible, thin grafts of even thickness. A CZM 500 kHz Visumax femto-second laser was used. Organ cultured donor grafts were mounted in an artifical anterior chamber with the endothelial side up and out. Posterior grafts of 7.8 mm diameter and 130 micron thickness were prepared by femto-second laser cutting. A standard DSAEK procedure was performed in 10 patients with Fuchs endothelial dystrophy. Patients were followed-up regularly and evaluated by measurement of complications, visual acuity, corneal thickness (Pentacam HR), and endothelial cell density. Femto-laser cutting of grafts and surgery was uncomplicated. Rebubbling was necessary in 5 of 10 cases (normally only in 1 of 20 cases). All grafts were attached and cleared up during the first few weeks. After six months, the average visual acuity was 0.30 (range: 0.16 to 0.50), corneal thickness was 0.58 mm (range 0.51 to 0.63), and endothelial cell density was 1.570 per sq. mm (range: 1.400 to 2.000 cells per sq. mm). The grafts were of uniform thickness, but substantial interface haze was present in most grafts. Posterior lamellar corneal grafts can be prepared from the endothelial side using a femto-second laser. All grafts were clear after 6 months with satisfying endothelial cell counts. Poor visual acuity caused by interface scatter was observed in most patients. Femto-second laser cutting parameters needs to be optimised to

Solvent effect on polystyrene surface roughness on top of QCM sensor

Energy Technology Data Exchange (ETDEWEB)

Sakti, Setyawan P., E-mail: sakti@ub.ac.id; Rahmawati, Eka; Robiandi, Fadli [Advanced System and Material Technology, Laboratory of Instrumentation and Measurement Department of Physics, Brawijaya University (Indonesia)

2016-03-11

Quartz Crystal Microbalance (QCM) has been used as a basis for many chemical sensors and biosensor. Its sensitivity to mass change which can detect a mass change on its surface down to sub ng/cm2 is one of its interesting aspects. Another interesting feature is its ability to work in liquid environment. However, there are many aspects which influence QCM sensor properties in contact with liquid. One of the aspects is surface roughness of the matrix layer where on top of it a biological sensitive layer will be immobilized. One of matrix layers in the immobilizing biological sensitive layer was polystyrene. Polystyrene was coated on the QCM sensor by using the spin coating method. During the coating process, polystyrene was solved using non-polar solvent. It is known that the physical and chemical properties of the solvent affect a transition process from soluble polymer becoming rigid polymer layer. In this work, we show that polystyrene solved in chloroform has a higher surface roughness compare to one solved in toluene, xylene, or tetrahydrofuran. Surface roughness of the polystyrene coating were measured using a non-contact profilometer. However, we also found that there is no difference on the electrical impedance of the QCM sensor coated with polystyrene resulted from differing solvent when the sensor was in contact with air and water. Thus, all of the mentioned solvent can be used to solve the polystyrene as a coating material for QCM sensor without affecting the electrical performance of the sensor, but the choice of the solution can be used as a simple method to control the difference roughness of the polystyrene coating.

Lamellar-crossing-structured Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposite for electrochemical supercapacitor materials

Energy Technology Data Exchange (ETDEWEB)

Wu, Qingnan [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Wen, Ming, E-mail: m_wen@tongji.edu.cn [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, Shanghai 200092 (China); Chen, Shipei [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Wu, Qingsheng [Department of Chemistry, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, Shanghai 200092 (China)

2015-10-15

Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} lamellar-crossing-nanostructure with a single lamellar spacing of ∼5 nm was effectively constructed through two-phase-interface reaction process followed by the CNTs crossed among the lamellar-nanostructured Ni(OH){sub 2}. The resultant nanocomposite can offer large active surface areas and short diffusion paths for electrons and ions, and is investigated as a potential pseudocapacitor electrode material for electrochemical energy storage applications. Electrochemical data demonstrate that the as-prepared nanocomposite exhibits a high specific capacitance of ∼1600 F g{sup −1} at the scan rate of 1 mV s{sup −1} in 6 M KOH solution at normal pressure and temperature, which is great higher than Ni(OH){sub 2} (∼1200 F g{sup −1}). Furthermore, Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposite shows a higher energy density (∼125 Wh kg{sup −1}, 2 A g{sup −1}) and has a slightly decrease of 5% in specific capacitance after 1000 continuous charge/discharge cycles. - Graphical abstract: As-constructed Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} lamellar-crossing-nanostructure exhibits remarkable enhancement in electrochemical stability and high specific capacity of ∼1600 F g{sup −1} at a scan rate of 1 mV s{sup −1}, suggesting promising potential for supercapacitor applications. - Highlights: • New designed lamellar-crossing-structured Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposites have been firstly reported in this work. • Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} lamellar-crossing-nanostructures show firm nanostructure and excellent electrochemical stability. • Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposites exhibit excellent specific capacitance. • Ni(OH){sub 2}/CNTs/Ni(OH){sub 2} nanocomposites have the potential application in electrochemical energy storage applications.

Electrochemical properties and diffusion of a redox active surfactant incorporated in bicontinuous cubic and lamellar phase

International Nuclear Information System (INIS)

Kostela, J.; Elmgren, M.; Almgren, M.

2005-01-01

The objective of this study was to investigate the electrochemical behaviour of the divalent redox active surfactant, N-cetyl-N'-methylviologen (CMV), in bicontinuous cubic and lamellar phases. The liquid crystalline phases were prepared from the system glycerolmonooleate (GMO)-water (and brine)-cationic surfactant. A comparison of the phase behaviour of GMO with the monovalent cetyltrimethylammonium bromide (CTAB) and the divalent CMV surfactant showed that the surfactants gave about the same effect at the same surface charge density. The electrochemical measurements were made with a mixture of CTAB and CMV as the surfactant. Cyclic voltammetry was used to study the electrochemistry of CMV incorporated in the cubic and lamellar phases that were spread on a gold electrode. The E 0 -values in the cubic samples were more negative (-0.55 V versus SCE) than in the lamellar samples (-0.53 V versus SCE). This can be explained by the higher charge density in the lamellar phase. The diffusion coefficients were also measured in the cubic phase. The mass transport is slowed down about fifty times in the cubic phase compared to in the pure electrolyte. The concentration dependence on the diffusion coefficient was also investigated. No electron hopping could be observed, which suggest that diffusional movement of the redox probe is the main source of charge transport. By placing the samples on a conducting glass slide, spectroelectrochemical investigations were performed. In the lamellar phase strong dimerization was detected at high concentration of viologen, but much less in the cubic phase

Electrochemical properties and diffusion of a redox active surfactant incorporated in bicontinuous cubic and lamellar phase

Energy Technology Data Exchange (ETDEWEB)

Kostela, J. [Uppsala University, Department of Physical Chemistry, Box 579, S-75123 Uppsala (Sweden)]. E-mail: johan.kostela@fki.uu.se; Elmgren, M. [Uppsala University, Department of Physical Chemistry, Box 579, S-75123 Uppsala (Sweden); Almgren, M. [Uppsala University, Department of Physical Chemistry, Box 579, S-75123 Uppsala (Sweden)

2005-05-30

The objective of this study was to investigate the electrochemical behaviour of the divalent redox active surfactant, N-cetyl-N'-methylviologen (CMV), in bicontinuous cubic and lamellar phases. The liquid crystalline phases were prepared from the system glycerolmonooleate (GMO)-water (and brine)-cationic surfactant. A comparison of the phase behaviour of GMO with the monovalent cetyltrimethylammonium bromide (CTAB) and the divalent CMV surfactant showed that the surfactants gave about the same effect at the same surface charge density. The electrochemical measurements were made with a mixture of CTAB and CMV as the surfactant. Cyclic voltammetry was used to study the electrochemistry of CMV incorporated in the cubic and lamellar phases that were spread on a gold electrode. The E {sup 0}-values in the cubic samples were more negative (-0.55 V versus SCE) than in the lamellar samples (-0.53 V versus SCE). This can be explained by the higher charge density in the lamellar phase. The diffusion coefficients were also measured in the cubic phase. The mass transport is slowed down about fifty times in the cubic phase compared to in the pure electrolyte. The concentration dependence on the diffusion coefficient was also investigated. No electron hopping could be observed, which suggest that diffusional movement of the redox probe is the main source of charge transport. By placing the samples on a conducting glass slide, spectroelectrochemical investigations were performed. In the lamellar phase strong dimerization was detected at high concentration of viologen, but much less in the cubic phase.

Microporous polystyrene particles for selective carbon dioxide capture.

Science.gov (United States)

Kaliva, Maria; Armatas, Gerasimos S; Vamvakaki, Maria

2012-02-07

This study presents the synthesis of microporous polystyrene particles and the potential use of these materials in CO(2) capture for biogas purification. Highly cross-linked polystyrene particles are synthesized by the emulsion copolymerization of styrene (St) and divinylbenzene (DVB) in water. The cross-link density of the polymer is varied by altering the St/DVB molar ratio. The size and the morphology of the particles are characterized by scanning and transmission electron microscopy. Following supercritical point drying with carbon dioxide or lyophilization from benzene, the polystyrene nanoparticles exhibit a significant surface area and permanent microporosity. The dried particles comprising 35 mol % St and 65 mol % DVB possess the largest surface area, ∼205 m(2)/g measured by Brunauer-Emmett-Teller and ∼185 m(2)/g measured by the Dubinin-Radushkevich method, and a total pore volume of 1.10 cm(3)/g. Low pressure measurements suggest that the microporous polystyrene particles exhibit a good separation performance of CO(2) over CH(4), with separation factors in the range of ∼7-13 (268 K, CO(2)/CH(4) = 5/95 gas mixture), which renders them attractive candidates for use in gas separation processes.

The ultra-structural organization of the elastic network in the intra- and inter-lamellar matrix of the intervertebral disc.

Science.gov (United States)

Tavakoli, J; Elliott, D M; Costi, J J

2017-08-01

The inter-lamellar matrix (ILM)-located between adjacent lamellae of the annulus fibrosus-consists of a complex structure of elastic fibers, while elastic fibers of the intra-lamellar region are aligned predominantly parallel to the collagen fibers. The organization of elastic fibers under low magnification, in both inter- and intra-lamellar regions, was studied by light microscopic analysis of histologically prepared samples; however, little is known about their ultrastructure. An ultrastructural visualization of elastic fibers in the inter-lamellar matrix is crucial for describing their contribution to structural integrity, as well as mechanical properties of the annulus fibrosus. The aims of this study were twofold: first, to present an ultrastructural analysis of the elastic fiber network in the ILM and intra-lamellar region, including cross section (CS) and in-plane (IP) lamellae, of the AF using Scanning Electron Microscopy (SEM) and second, to -compare the elastic fiber orientation between the ILM and intra-lamellar region. Four samples (lumbar sheep discs) from adjacent sections (30μm thickness) of anterior annulus were partially digested by a developed NaOH-sonication method for visualization of elastic fibers by SEM. Elastic fiber orientation and distribution were quantified relative to the tangential to circumferential reference axis. Visualization of the ILM under high magnification revealed a dense network of elastic fibers that has not been previously described. Within the ILM, elastic fibers form a complex network, consisting of different size and shape fibers, which differed to those located in the intra-lamellar region. For both regions, the majority of fibers were oriented near 0° with respect to tangential to circumferential (TCD) direction and two minor symmetrical orientations of approximately±45°. Statistically, the orientation of elastic fibers between the ILM and intra-lamellar region was not different (p=0.171). The present study used

Oligosaccharides and glycolipids addition in charged lamellar phases; Addition d`oligosaccharides et de glycolipides dans des phases lamellaires chargees

Energy Technology Data Exchange (ETDEWEB)

Ricoul, F

1997-09-26

The aim of this work is to study the addition of oligosaccharides and glycolipids in lamellar phases of the cationic surfactant DDAB (di-dodecyl-dimethyl-ammonium bromide). Two steps have been followed: the determination of phases prisms and the thermodynamic interpretation in terms of molecular interactions. In order to characterize these systems, two new experimental small angle scattering methods have been perfected: 1) a neutron scattering contrast variation method which allows to study the adsorption of aqueous solution in bilayers and 2) a capillary concentration gradient method to establish directly and quantitatively the phases diagrams of ternary systems by X rays scattering. It has been pointed out that the oligosaccharides induce a depletion attractive force on the lamellar-lamellar equilibrium of the DDAB when they are excluded of the most concentrated phase. For the two studied glycolipids: 2-O lauroyl-saccharose and N-lauroyl N-nonyl lactitol, the ternary phase diagrams water-DDAB-glycolipid have been established in terms of temperature. Critical points at ambient temperature have been given. The osmotic pressure in concentrated lamellar phases has been measured. It has been shown that glycolipids increase the hydration repulsion at short distance and that the electrostatic repulsion is outstanding and unchanged at high distance if there is at less 1 mole percent of ionic surfactant. In a dilute solution, glycolipids decrease the maximum swelling of lamellar phases, with a competition between the lamellar phase and the micellae dilute phase for water. (O.M.). 165 refs.

Electroclinic effect in the chiral lamellar α phase of a lyotropic liquid crystal

Science.gov (United States)

Harjung, Marc D.; Giesselmann, Frank

2018-03-01

In thermotropic chiral Sm -A* phases, an electric field along the smectic layers breaks the D∞ symmetry of the Sm -A* phase and induces a tilt of the liquid crystal director. This so-called electroclinic effect (ECE) was first reported by Garoff and Meyer in 1977 and attracted substantial scientific and technological interest due to its linear and submicrosecond electro-optic response [S. Garoff and R. B. Meyer, Phys. Rev. A 19, 338 (1979), 10.1103/PhysRevA.19.338]. We now report the observation of an ECE in the pretransitional regime from a lyotropic chiral lamellar Lα* phase into a lyo-Sm -C* phase, the lyotropic analog to the thermotropic Sm -C* phase which was recently discovered by Bruckner et al. [Angew. Chem. Int. Ed. 52, 8934 (2013), 10.1002/anie.201303344]. We further show that the observed ECE has all signatures of its thermotropic counterpart, namely (i) the effect is chiral in nature and vanishes in the racemic Lα phase, (ii) the effect is essentially linear in the sign and magnitude of the electric field, and (iii) the magnitude of the effect diverges hyperbolically as the temperature approaches the critical temperature of the second order tilting transition. Specific deviations between the ECEs in chiral lamellar and chiral smectic phases are related to the internal field screening effect of electric double layers formed by inevitable ionic impurities in lyotropic phases.

The surface modification of polystyrene

International Nuclear Information System (INIS)

Tremlett, C.

2000-03-01

Polymers have ideal bulk properties for many applications. However, adhesion to many polymers is poor without surface pretreatment. This can result, for example, in peeling paint and printing, adhesive joint failure and bio-incompatibility. In applications such as painting, printing, adhesive bonding and biocompatibility, various cleaning or surface chemical modifications may be employed. A commodity polymer where pretreatment is sometimes needed is polystyrene. This project investigated, in detail, the effects of a novel method of modification namely mediated electrochemical oxidation (MEO), as a mode of surface modification on polystyrene and a comparison was made with other polymers. The resulting modification was investigated using a range of surface analysis techniques to obtain complementary information. These included, X-ray photoelectron spectroscopy, contact angles, static secondary ion mass spectrometry, atomic force microscopy, chemical derivatization, scanning electron microscopy, attenuated total reflection Fourier Transform infrared spectroscopy and composite lap shear joint testing. It has been shown that MEO modifies the surface of polystyrene introduced oxygen mainly as hydroxyl groups, and a small number of carbonyl groups, that are positioned only on the backbone hydrocarbon chain. This modification improved adhesion, was stable and samples could be stored in aqueous media. The resulting hydroxylation was further derivatized using an amino acid to provide a specialised surface. This was very different from the multiple oxygen functionalities introduced in the comparison studies by UV/ozone and plasma treatments. (author)

Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

Science.gov (United States)

Chen, Kuizhi; Pan, Sujuan; Zhuang, Xuemei; Lv, Hafei; Que, Shoulin; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-07-01

1-2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G n -DSiPc(CN)4 n , (G n = n-generation dendrimer, n = 1-2)) were synthesized. Their structures were characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Polymeric nanoparticles (G n -DSiPc(CN)4 n /m) were formed through encapsulating G n -DSiPc(CN)4 n into three monomethoxyl poly(ethylene glycol)-poly(ɛ-caprolactone) diblock copolymers (MPEG-PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G n -DSiPc(CN)4 n and G n -DSiPc(CN)4 n /m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G n -DSiPc(CN)4 n /m were lower than the corresponding free dendrimer phthalocyanines. G n -DSiPc(CN)4 n encapsulated into MPEG-PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG2000-PCL2000 micelles was about 70 nm, which decreased when loaded with G n -DSiPc(CN)4 n .

Enhanced sensitivity of a microfabricated resonator using a graphene-polystyrene bilayer membrane

Energy Technology Data Exchange (ETDEWEB)

Yun, Minhyuk; Lee, Eunho; Cho, Kilwon; Jeon, Sangmin, E-mail: jeons@postech.ac.kr [Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), Pohang (Korea, Republic of)

2014-08-18

A graphene layer was synthesized using chemical vapor deposition methods and a polystyrene solution was spin-cast onto the graphene film. The graphene-polystyrene bilayer membrane was attached between the two tines of a microfabricated quartz tuning fork (QTF). The modulus of the graphene-polystyrene bilayer was measured to be twice that of a pristine polystyrene membrane. Exposure of the membrane-coated QTF to ethanol vapor decreased the resonance frequency of the microresonator. The bilayer membrane-coated QTF produced a frequency change that was three times the change obtained using a polystyrene membrane-coated QTF, with a lower degree of degradation in the Q factor. The limit of detection of the bilayer membrane-coated QTF to ethanol vapor was determined to be 20 ppm.

The Study of the Microbes Degraded Polystyrene

Directory of Open Access Journals (Sweden)

Zhi-Long Tang

2017-01-01

Full Text Available Under the observation that Tenebrio molitor and Zophobas morio could eat polystyrene (PS, we setup the platform to screen the gut microbes of these two worms. To take advantage of that Tenebrio molitor and Zophobas morio can eat and digest polystyrene as its diet, we analyzed these special microbes with PS plate and PS turbidity system with time courses. There were two strains TM1 and ZM1 which isolated from Tenebrio molitor and Zophobas morio, and were identified by 16S rDNA sequencing. The results showed that TM1 and ZM1 were cocci-like and short rod shape Gram-negative bacteria under microscope. The PS plate and turbidity assay showed that TM1 and ZM1 could utilize polystyrene as their carbon sources. The further study of PS degraded enzyme and cloning warrants our attention that this platform will be an excellent tools to explore and solve this problem.

Using X-PEEM to study biomaterials: Protein and peptide adsorption to a polystyrene-poly(methyl methacrylate)-b-polyacrylic acid blend

Energy Technology Data Exchange (ETDEWEB)

Leung, Bonnie O. [Chemistry and Chemical Biology, BIMR, McMaster University, Hamilton, ON, Canada L8S 4M1 (Canada); Hitchcock, Adam P., E-mail: aph@mcmaster.ca [Chemistry and Chemical Biology, BIMR, McMaster University, Hamilton, ON, Canada L8S 4M1 (Canada); Cornelius, Rena M.; Brash, John L. [School of Biomedical Engineering, McMaster University, Hamilton, ON, Canada L8S 4M1 (Canada); Scholl, Andreas; Doran, Andrew [Advanced Light Source, Berkeley Lab, Berkeley, CA 94720 (United States)

2012-10-15

Highlights: Black-Right-Pointing-Pointer We review applications of synchrotron X-PEEM to biomaterials. Black-Right-Pointing-Pointer We report characterization of a PS/PMMA-b-PAA blend surface by AFM and X-PEEM. Black-Right-Pointing-Pointer We report quantitative mapping of protein (HSA) and peptide adsorption on PS/PMMA-b-PAA. Black-Right-Pointing-Pointer We report how this adsorption changes with pH. -- Abstract: Recent synchrotron-based soft X-ray photoemission electron microscopy (X-PEEM) studies of protein and peptide interaction with phase segregated and patterned polymer surfaces in the context of optimization of candidate biomaterials are reviewed and a study of a new system is reported. X-PEEM and atomic force microscopy (AFM) were used to investigate the morphology of a phase-segregated thin film of a polystyrene/poly(methyl methacrylate)-b-polyacrylic acid (PS/PMMA-PAA) blend, and its interactions with negatively charged human serum albumin (HSA) and positively charged SUB-6 (a cationic antimicrobial peptide, RWWKIWVIRWWR-NH{sub 2}) at several pHs. At neutral pH, where the polymer surface is partially negatively charged, HSA and SUB-6 peptide showed contrasting adsorption behavior which is interpreted in terms of differences in their electrostatic interactions with the polymer surface.

Electromechanical responses of poly(3-thiopheneacetic acid/acrylonitrile-butadiene rubbers

Directory of Open Access Journals (Sweden)

2008-12-01

Full Text Available Acrylonitrile-butadiene rubber (NBR and blends of poly(3-thiopheneacetic acid/ acrylonitrile-butadiene rubber, P3TAA/NBR, were fabricated, and the electrorheological properties, dielectric, and electrical conductivities were investigated . The electrorheological properties were determined under an oscillatory shear mode in a frequency range of 0.1 to 100 rad/s at various electric field strengths, from 0 to 2 kV/mm, at a fixed 27°C to observe the effects of acrylonitrile content (ACN in the rubber systems and the conductive particle concentration in the blends. For the pure rubber systems, the storage modulus response (ΔG′ is linearly dependent on its dielectric constant (ε′, and increases with the ACN content. For the NBR/P3TAA blends, the storage modulus response varies nonlinearly with the dielectric constant. The bending responses of the rubbers and the blends were investigated in a vertical cantilever fixture. For the pure rubber system, the bending angle and the dielectrophoresis force vary linearly with electric field strength. For the blend system, the bending angle and the dielectrophoresis force vary nonlinearly with electric field strength.

Morphological abnormalities and apoptosis in lamellar tissue of equines after intestinal obstruction and treatment with hydrocortisone

Directory of Open Access Journals (Sweden)

L.M Laskoski

2010-12-01

Full Text Available Four experimental groups of equines were used in order to study morphological abnormalities and apoptosis in lamellar tissue. Group Cg (control was composed of animals without any surgical procedure; group Ig (instrumented, animals that underwent enterotomy; group Tg (treated, animals that were subjected to intestinal obstruction and were treated with hydrocortisone; and group Ug (untreated, animals that were subjected to intestinal obstruction without treatment. The lamellar tissue was analyzed regarding the presence of tissue abnormalities and apoptosis. No morphological abnormalities were observed in animals of surgical groups, and no difference in apoptosis was observed between groups. It was concluded that intestinal obstruction allowed laminitis to develop, probably by systemic activation, and that the maneuvers performed in the enterotomy aggravated the process. Hydrocortisone did not aggravate the lesions of the lamellar tissue

Formation of core (polystyrene)-shell (polybenzimidazole) nanoparticles using sulfonated polystyrene as template.

Science.gov (United States)

Hazarika, Mousumi; Arunbabu, Dhamodaran; Jana, Tushar

2010-11-15

We report formation of core (polystyrene)-shell (polybenzimidazole) nanoparticles from a new blend system consisting of an amorphous polymer polybenzimidazole (PBI) and an ionomer sodium salt of sulfonated polystyrene (SPS-Na). The ionomer used for the blending is spherical in shape with sulfonate groups on the surface of the particles. An in depth investigation of the blends at various sulfonation degrees and compositions using Fourier transform infrared (FT-IR) spectroscopy provides direct evidence of specific hydrogen bonding interactions between the N-H groups of PBI and the sulfonate groups of SPS-Na. The disruption of PBI chains self association owing to the interaction between the functional groups of these polymer pairs is the driving force for the blending. Thermodynamical studies carried out by using differential scanning calorimeter (DSC) establish partially miscible phase separated blending of these polymers in a wider composition range. The two distinguishable glass transition temperatures (T(g)) which are different from the neat components and unaltered with the blends composition attribute that the domain size of heterogeneity (d(d)) of the blends is >20 nm since one of the blend component (SPS-Na particle) diameter is ∼70 nm. The diminish of PBI chains self association upon blending with SPS-Na particles and the presence of invariant T(g)'s of the blends suggest the wrapping of PBI chains over the SPS-Na spherical particle surface and hence resulting a core-shell morphology. Transmission electron microscopy (TEM) study provides direct evidence of core-shell nanoparticle formation; where core is the polystyrene and shell is the PBI. The sulfonation degree affects the blends phase separations. The higher degree of sulfonation favors the disruption of PBI self association and thus forms partially miscible two phases blends with core-shell morphology. Copyright © 2010 Elsevier Inc. All rights reserved.

Reverse osmosis desalination of chitosan cross-linked graphene oxide/titania hybrid lamellar membranes.

Science.gov (United States)

Deng, Hui; Sun, Penzhan; Zhang, Yingjiu; Zhu, Hongwei

2016-07-08

With excellent mass transport properties, graphene oxide (GO)-based lamellar membranes are believed to have great potential in water desalination. In order to quantify whether GO-based membranes are indeed suitable for reverse osmosis (RO) desalination, three sub-micrometer thick GO-based lamellar membranes: GO-only, reduced GO (RGO)/titania (TO) nanosheets and RGO/TO/chitosan (CTS) are prepared, and their RO desalination performances are evaluated in a home-made RO test apparatus. The photoreduction of GO by TO improves the salt rejection, which increases slowly with the membrane thickness. The RGO/TO/CTS hybrid membranes exhibit higher rejection rates of only about 30% (greater than threefold improvement compared with a GO-only membrane) which is still inferior compared to other commercial RO membranes. The low rejection rates mainly arise from the pressure-induced weakening of the ion-GO interlayer interactions. Despite the advantages of simple, low-cost preparation, high permeability and selectivity of GO-based lamellar membranes, as the current desalination performances are not high enough to afford practical application, there still remains a great challenge to realize high performance separation membranes for water desalination applications.

SYNTHESIS OF STYRENE-BUTADIENE STATISTIC COPOLYMERS CONTAINING MAGNESIUM INITIATOR

Directory of Open Access Journals (Sweden)

A. V. Firsova

2015-01-01

Full Text Available The article discusses the use of organomagnesium initiators in the synthesis of styrene-butadiene random copolymer (SBR obtained solution polymerization and their influence on the properties of rubber. Selected organic magnesium dialkyl initiator is combined with a modifier, which is a mixed alkoxide of an alkali and alkaline earth metals, which allows to control the micr ostructure of the diene polymer and its molecular weight characteristics. Alcohol derivatives selected high-boiling alcohols tetra (hydroxypropyl ethylenediamine (lapromol 294 and tetrahydrofurfuryl alcohol (TGFS. Selection of high-boiling alcohols due to the fact that the destruction of alkoxide with aqueous polymer degassing they do not fall into the return solvent and almost fall into the exact water. The metal components of alkoxides are lithium, sodium, potassium, magnesium and calcium. The resulting solutions are stable when stored modifier t hroughout the year even at -40 °C. The scheme of obtaining the new catalyst systems based organomagnesium and alcoxide of alkali and alkaline earth metals, which yields as functionalized SBR with a statistical and a distribution block of butadiene and styrene was developed. The process of copolymerization with styrene to butadiene organomagnesium initiators as using an organolithium compound (n-butyllithium was carried out, and without it. Found that the addition of n-butyllithium in the reaction mixture leads to a sharp increase in the rate of reaction. The results of studies of the effect of composition of the initiator system on the structure of diene polymers. It was revealed that a mixed initiator system affords a high conversion of monomers (to 90 % in 1 hour 1,2-polybutadiene content increased to 60 %. The process of polymerization of only a mixture of organomagnesium initiators and alcoxide of alkali and alkaline earth metals are not actively proceeds, conversion of the monomers reaches to 90 % in 4 hours, the microstructure

Radiation crosslinked block copolymer blends with improved impact resistance

International Nuclear Information System (INIS)

Saunders, F.L.; Pelletier, R.R.

1976-01-01

Polymer blends having high impact resistance after mechanical working are produced by blending together a non-elastomeric monovinylidene aromatic polymer such as polystyrene with an elastomeric copolymer, such as a block copolymer of styrene and butadiene, in the form of crosslinked, colloidal size particles

Behavior of positronium in polystyrene and its derivatives

International Nuclear Information System (INIS)

Honda, Y.; Watanabe, M.; Tashiro, M.; Terashima, Y.; Miyamoto, K.; Kimura, N.; Tagawa, S.

2003-01-01

The polystyrene, poly(4-bromostyrene) and poly(4-vinylphenol) are investigated using slow positron beam based on electron linac. There was a difference in the intensity of long-lived component of lifetime in o-Ps (τ 3 ). The S-parameter and the intensity of τ 3 were strongly influenced by the presence of the substituents of polystyrene. In thin films, irradiation effect caused by positron beam was observed

Combined effect of gamma radiation and stress cracking in polystyrene

International Nuclear Information System (INIS)

Amorim, Fernando A.; Rabello, Marcelo S.; Silva, Leonardo G.A.

2011-01-01

This study aimed to evaluate the combined effect of gamma radiation and stress cracking in polystyrene. Three different grades of polystyrene were analysed. The material was submitted to tensile tests and relaxation, analysis of molecular weight and determination of crosslinking. The results showed an increase in tensile strength in the specimens that had been exposed to radiation. The higher the molecular weight polystyrene showed better mechanical properties and after suffering the effects of gamma radiation there was an increase of 5.67% in the resistance to stress cracking effects. (author)

Rapid Ordering in "Wet Brush" Block Copolymer/Homopolymer Ternary Blends.

Science.gov (United States)

Doerk, Gregory S; Yager, Kevin G

2017-12-26

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed via self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-block-poly(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the "wet brush" regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved within minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. These results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order-disorder transition through low molecular weight homopolymer blending.

Particle reinforced composites from acrylamide modified blend of styrene-butadiene and natural rubber

Science.gov (United States)

Blends of styrene-butadiene rubber and natural rubber that provide balanced properties were modified with acrylamide and reinforced with soy protein particles. The rubber composites show improved mechanical properties. Both modified rubber and composites showed a faster curing rate. The crosslinking...

Synthesis of polystyrene, poly(styrene/4-vinylpyridine), poly(p-nitrostyrene) and poly(p-aminostyrene)-coated silica and their extraction capabilities for amphetamine

International Nuclear Information System (INIS)

Sun Changmei; Zhang Shuanhong; Qu Rongjun; Sun Tao; Zhang Ying; Zhang Xiang; Song Jingyang

2010-01-01

Several novel organic-inorganic hybrid materials, including polystyrene-coated silica (SG-PS), poly(styrene/4-vinylpyridine)-coated silica (SG-PVP), poly(p-nitrostyrene)-coated silica (SG-PS-NO 2 ) and poly(p-aminostyrene)-coated silica (SG-PS-NH 2 ), were synthesized in order to improve the extraction methods of harmful stimulants via solid phase extraction. The materials were characterized using infrared spectra (IR), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) surface area measurement and thermogravimetric analysis (TG). The application of the new materials in solid phase extraction columns to extract methamphetamine revealed that the extraction capability of poly(styrene/4-vinylpyridine)-coated silica is the best among the four materials, which provides novel supporter materials for extracting amphetamine-derived drugs.

Synthesis of polystyrene, poly(styrene/4-vinylpyridine), poly(p-nitrostyrene) and poly(p-aminostyrene)-coated silica and their extraction capabilities for amphetamine

Energy Technology Data Exchange (ETDEWEB)

Sun Changmei; Zhang Shuanhong [School of Chemistry and Materials Science, Ludong University, Yantai, Shandong 264025 (China); Qu Rongjun, E-mail: qurongjun@eyou.com [School of Chemistry and Materials Science, Ludong University, Yantai, Shandong 264025 (China); Sun Tao; Zhang Ying; Zhang Xiang; Song Jingyang [School of Chemistry and Materials Science, Ludong University, Yantai, Shandong 264025 (China)

2010-11-01

Several novel organic-inorganic hybrid materials, including polystyrene-coated silica (SG-PS), poly(styrene/4-vinylpyridine)-coated silica (SG-PVP), poly(p-nitrostyrene)-coated silica (SG-PS-NO{sub 2}) and poly(p-aminostyrene)-coated silica (SG-PS-NH{sub 2}), were synthesized in order to improve the extraction methods of harmful stimulants via solid phase extraction. The materials were characterized using infrared spectra (IR), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) surface area measurement and thermogravimetric analysis (TG). The application of the new materials in solid phase extraction columns to extract methamphetamine revealed that the extraction capability of poly(styrene/4-vinylpyridine)-coated silica is the best among the four materials, which provides novel supporter materials for extracting amphetamine-derived drugs.

Partially-Functionalized Isotactic Polystyrene with Blocky Comonomer Segments

Science.gov (United States)

Siegel, Ariel; Powers, Wayne; Ryu, Chang Y.

2012-02-01

Isotactic polystyrenes (iPSs) have been functionalized in solution, while the accessibility of functionalizing agent is limited by the formation of crystalline domains at various temperatures. The chemical system used is the borylated isotactic polystyrene system, and we investigated the temperature effects on reaction kinetics to ultimately control the blockiness of borylated segments in the resulting copolymer. The chemical composition of partially borylated iPS reaches a steady state that is dependent on temperature. This synthesis has been performed at many different temperatures, with different steady states being reached at different temperatures. Further analysis by differential scanning calorimetry (DSC) has shown that the higher temperature reactions have greater effect on breaking down the crystal lattice structure of the isotactic polystyrene. As a result, the lower temperature reactions affect the crystalline structure less, and the resulting copolymer has more blockiness.

Polystyrene nanoparticles activate ion transport in human airway epithelial cells

Directory of Open Access Journals (Sweden)

McCarthy J

2011-06-01

Full Text Available J McCarthy1, X Gong2, D Nahirney2, M Duszyk2, MW Radomski11School of Pharmacy and Pharmaceutical Sciences, Panoz Institute, Trinity College Dublin, Dublin, Ireland; 2Department of Physiology, University of Alberta, Edmonton, Alberta, CanadaBackground: Over the last decade, nanotechnology has provided researchers with new nanometer materials, such as nanoparticles, which have the potential to provide new therapies for many lung diseases. In this study, we investigated the acute effects of polystyrene nanoparticles on epithelial ion channel function.Methods: Human submucosal Calu-3 cells that express cystic fibrosis transmembrane conductance regulator (CFTR and baby hamster kidney cells engineered to express the wild-type CFTR gene were used to investigate the actions of negatively charged 20 nm polystyrene nanoparticles on short-circuit current in Calu-3 cells by Ussing chamber and single CFTR Cl- channels alone and in the presence of known CFTR channel activators by using baby hamster kidney cell patches.Results: Polystyrene nanoparticles caused sustained, repeatable, and concentration-dependent increases in short-circuit current. In turn, these short-circuit current responses were found to be biphasic in nature, ie, an initial peak followed by a plateau. EC50 values for peak and plateau short-circuit current responses were 1457 and 315.5 ng/mL, respectively. Short-circuit current was inhibited by diphenylamine-2-carboxylate, a CFTR Cl- channel blocker. Polystyrene nanoparticles activated basolateral K+ channels and affected Cl- and HCO3- secretion. The mechanism of short-circuit current activation by polystyrene nanoparticles was found to be largely dependent on calcium-dependent and cyclic nucleotide-dependent phosphorylation of CFTR Cl- channels. Recordings from isolated inside-out patches using baby hamster kidney cells confirmed the direct activation of CFTR Cl- channels by the nanoparticles.Conclusion: This is the first study to identify

Adsorption of dimeric surfactants in lamellar silicates

Energy Technology Data Exchange (ETDEWEB)

Balcerzak, Mateusz; Pietralik, Zuzanna [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Domka, Ludwik [Department of Metalorganic Chemistry, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznań (Poland); Skrzypczak, Andrzej [Institute of Chemical Technology, Poznań University of Technology, Berdychowo 4, 60-965 Poznań (Poland); Kozak, Maciej, E-mail: mkozak@amu.edu.pl [Department of Macromolecular Physics, Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)

2015-12-01

Highlights: • The intercalation of dimeric surfactants changed the morphology of MMT samples. • XRD indicated structures formed by surfactant molecules in interlayer space. • The four-step thermal decomposition of dimeric surfactant, confirms intercalation. - Abstract: The adsorption of different types of cationic surfactants in lamellar silicates changes their surface character from hydrophilic to hydrophobic. This study was undertaken to obtain lamellar silicates modified by a series of novel dimeric (gemini) surfactants of different length alkyl chains and to characterise these organophilised materials. Synthetic sodium montmorillonite SOMASIF® ME 100 (M) and enriched bentonite of natural origin (Nanoclay – hydrophilic bentonite®) were organophilised with dimeric (gemini) surfactants (1,1′-(1,4-butanediyl)bis(alkoxymethyl)imidazolium dichlorides). As a result of surfactant molecule adsorption in interlamellar space, the d-spacing (d{sub 001}) increased from 0.97 nm (for the anhydrous structure) to 2.04 nm. A Fourier transform infrared spectroscopy (FTIR) analysis of the modified systems reveals bands assigned to the stretching vibrations of the CH{sub 2} and CH{sub 3} groups and the scissoring vibrations of the NH group from the structure of the dimeric surfactants. Thermogravimetric (TG) and derivative thermogravimetric (DTG) studies imply a four-stage process of surfactant decomposition. Scanning electron microscopy (SEM) images provide information on the influence of dimeric surfactant intercalation into the silicate structures. Particles of the modified systems show a tendency toward the formation of irregularly shaped agglomerates.

Human plasma fibrinogen adsorption and platelet adhesion to polystyrene.

Science.gov (United States)

Tsai, W B; Grunkemeier, J M; Horbett, T A

1999-02-01

The purpose of this study was to further investigate the role of fibrinogen adsorbed from plasma in mediating platelet adhesion to polymeric biomaterials. Polystyrene was used as a model hydrophobic polymer; i.e., we expected that the role of fibrinogen in platelet adhesion to polystyrene would be representative of other hydrophobic polymers. Platelet adhesion was compared to both the amount and conformation of adsorbed fibrinogen. The strategy was to compare platelet adhesion to surfaces preadsorbed with normal, afibrinogenemic, and fibrinogen-replenished afibrinogenemic plasmas. Platelet adhesion was determined by the lactate dehydrogenase (LDH) method, which was found to be closely correlated with adhesion of 111In-labeled platelets. Fibrinogen adsorption from afibrinogenemic plasma to polystyrene (Immulon I(R)) was low and polystyrene preadsorbed with fibrinogen-replenished afibrinogenemic plasma. Addition of even small, subnormal concentrations of fibrinogen to afibrinogenemic plasma greatly increased platelet adhesion. In addition, surface-bound fibrinogen's ability to mediate platelet adhesion was different, depending on the plasma concentration from which fibrinogen was adsorbed. These differences correlated with changes in the binding of a monoclonal antibody that binds to the Aalpha chain RGDS (572-575), suggesting alteration in the conformation or orientation of the adsorbed fibrinogen. Platelet adhesion to polystyrene preadsorbed with blood plasma thus appears to be a strongly bivariate function of adsorbed fibrinogen, responsive to both low amounts and altered states of the adsorbed molecule. Copyright 1999 John Wiley & Sons, Inc.

X-ray excited luminescence of polystyrene composites loaded with SrF{sub 2} nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Demkiv, T.M.; Halyatkin, O.O.; Vistovskyy, V.V. [Ivan Franko National University of Lviv, 8a Kyryla i Mefodiya St., 79005 Lviv (Ukraine); Hevyk, V.B. [Ivano-Frankivsk National Technical University of Oil and Gas, 15 Karpatska St., 76019 Ivano-Frankivsk (Ukraine); Yakibchuk, P.M. [Ivan Franko National University of Lviv, 8a Kyryla i Mefodiya St., 79005 Lviv (Ukraine); Gektin, A.V. [Institute for Scintillation Materials, NAS of Ukraine, 60 Lenina Ave, 61001 Kharkiv (Ukraine); Voloshinovskii, A.S. [Ivan Franko National University of Lviv, 8a Kyryla i Mefodiya St., 79005 Lviv (Ukraine)

2017-03-01

The polystyrene film nanocomposites of 0.3 mm thickness with embedded SrF{sub 2} nanoparticles up to 40 wt% have been synthesized. The luminescent and kinetic properties of the polystyrene composites with embedded SrF{sub 2} nanoparticles upon the pulse X-ray excitation have been investigated. The luminescence intensity of the pure polystyrene scintillator film significantly increases when it is loaded with the inorganic SrF{sub 2} nanoparticles. The film nanocomposites show fast (∼2.8 ns) and slow (∼700 ns) luminescence decay components typical for a luminescence of polystyrene activators (p-Terphenyl and POPOP) and SrF{sub 2} nanoparticles, respectively. It is revealed that the fast decay luminescence component of the polystyrene composites is caused by the excitation of polystyrene by the photoelectrons escaped from the nanoparticles due to photoeffect, and the slow component is caused by reabsorption of the self-trapped exciton luminescence of SrF{sub 2} nanoparticles by polystyrene.

Improved synthesis of polystyrene-poly(ethylene oxide)-heparin block copolymers

NARCIS (Netherlands)

Vulic, I.; Loman, A.J.B.; Feijen, Jan; Okano, T.; Kim, S.W.

1990-01-01

A novel procedure for the synthesis of block copolymers composed of a hydrophobic block of polystyrene, a hydrophilic block of poly(ethylene oxide) and a bioactive block of nitrous acid-degraded heparin was developed. Amino-semitelechelic polystyrene was prepared by anionic polymerization of styrene

Incorporation of Nanohybrid Films of Silica into Recycled Polystyrene Matrix

Directory of Open Access Journals (Sweden)

Genoveva Hernández-Padrón

2015-01-01

Full Text Available An alternative for the reutilization of polystyrene waste containers consisting in creating a hybrid material made of SiO2 nanoparticles embedded in a matrix of recycled polystyrene (PSR has been developed. Recycled polystyrene functionalized (PSRF was used to influence the morphological and antifog properties by the sol-gel synthesis of nanohybrid silica. To this end, silica nanoparticles were produced from alkoxide precursors in the presence of recycled polystyrene. The functionalization of this polymeric matrix was with the purpose of uniting in situ carboxyl and silanol groups during the sol-gel process. In this way, opaque or transparent solid substrates can be obtained, with each of these endowed with optical conditions that depend on the amount of reactants employed to prepare each nanohybrid specimen. The nanohybrids were labelled as SiO2/PSR (HPSR and SiO2/PSRF (HPSRF and their properties were then compared to those of commercial polystyrene (PS. All the prepared samples were used for coating glass substrates. The hydrophobicity of the resultant coatings was determined through contact angle measurement. The nanohybrid materials were characterized by FT-IR and 1H-NMR techniques. Additionally, TGA and SEM were employed to determine their thermal and textural properties.

A pulsed field gradient NMR study of a ternary homopolymer/diblock copolymer blend in the bicontinuous microemulsion phase

Czech Academy of Sciences Publication Activity Database

Gröger, S.; Rittig, F.; Stallmach, F.; Almdal, K.; Štěpánek, Petr; Papadakis, C. M.

2002-01-01

Roč. 117, č. 1 (2002), s. 396-406 ISSN 0021-9606 R&D Projects: GA AV ČR IAA1050902 Institutional research plan: CEZ:AV0Z4050913 Keywords : polymer blends * diblock copolymer * dynamic light scattering Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.998, year: 2002

Research and application of fuzzy subtractive clustering model on tensile strength of radiation vulcanization for nitrile-butadiene rubber

International Nuclear Information System (INIS)

Zuo Duwen; Wang Hong; Zhu Nankang

2010-01-01

By use of fuzzy subtractive clustering model, the relationship between tensile strength of radiation vulcanization of NBRL (Nitrile-butadiene rubber latex) and irradiation parameters have been investigated. The correlation coefficient was calculated to be 0.8222 in the comparison of experimental data to the predicted data. It was obvious that fuzzy model identification method is not only high precision with small computation, but also easy to be used. It can directly supply the evolution of tensile strength of NBR by fuzzy modeling method in radiation vulcanization process for nitrile-butadiene rubber. (authors)

Inhalation developmental toxicology studies of 1,3-butadiene in the rat: Final report

Energy Technology Data Exchange (ETDEWEB)

Hackett, P.L.; Sikov, M.R.; Mast, T.J.; Brown, M.G.; Buschbom, R.L.; Clark, M.L.; Decker, J.R.; Evanoff, J.J.; Rommereim, R.L.; Rowe, S.E.; Westerberg, R.B.

1987-11-01

Maternal toxicity, reproductive performance and developmental toxicology were evaluated in Sprague-Dawley-derived rats during and following 6 hours/day, whole-body, inhalation exposures to 0, 40, 200, and 1000 ppM of 1,3-butadiene. The female rats (Ns = 24 to 28), which had mated with unexposed males, were exposed to the chemical from 6 through 15 dg and sacrificed on 20 dg. Maternal animals were weighed prior to mating and on 0, 6, 11, 16 and 20 dg; the rats were observed for mortality, morbidity and signs of toxicity during exposure and examined for gross tissue abnormalities at necropsy. Live fetuses were weighed and subjected to external, visceral and skeletal examinations to detect growth retardation and morphologic anomalies. There were no significant differences among treatment groups in maternal body weights or extragestational weights of rats exposed to 1,3-butadiene concentrations of 40 or 200 ppM, but, in animals exposed to 1000 ppM, significantly depressed body weight gains were observed during the first 5 days of exposure and extragestational weight gains tended to be lower than control values. These results, and the absence of clinical signs of toxicity, were considered to indicate that there was no maternal toxicity at exposure levels of 200 ppM or lower. The percentage of pregnant animals and the number of litters with live fetuses were unaffected by treatment. Under the conditions of this exposure regimen, there was no evidence for a teratogenic response to 1,3-butadiene exposure.

Creep mechanisms of fully-lamellar TiAl based upon interface sliding

International Nuclear Information System (INIS)

Hsiung, L.M.; Nieh, T.G.

1999-01-01

Deformation mechanisms of fully lamellar TiAl with a refined microstructure (γ lamellae: 100 approximately 300 nm thick, α 2 lamellae: 10 approximately 50 nm thick) crept at 760 C have been investigated. As a result of a fine structure, the motion and multiplication of lattice dislocations within both γ and α 2 lamellae are limited at low creep stresses ( 2 and γ/γ interfaces (i.e., interface sliding) is proposed to be the dominant deformation mechanism at low stresses. Lattice dislocations impinged on lamellar interfaces are found to be the major obstacles impeding the motion of interfacial dislocations. The number of impinged lattice dislocations increases as the applied stress increases and, subsequently, causes the pileup of interfacial dislocations along the interfaces. Accordingly, deformation twinning activated by the pileup of interfacial dislocations is proposed to be the dominant deformation mechanism at high stresses (>400 MPa)

Microscopy evidence of the face-centered cubic arrangement of monodisperse polystyrene nanospheres

Energy Technology Data Exchange (ETDEWEB)

Zhang Hui [School of Science, Beijing Jiaotong University, Beijing 100044 (China)]. E-mail: zhanghui14305@sohu.com; Duan Renguan [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Li Fan [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Tang Qing [Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100080 (China); Li Wenchao [Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083 (China)

2007-07-01

This paper reports a scanning electron microscopy (SEM) investigation of polystyrene artificial opal achieved through self-assembly of monodisperse polystyrene nanospheres with a diameter of 250 nm from colloidal suspension after being ambient dried. A detailed analysis of the SEM images verifies that the face-centered cubic (fcc) phase is the most stable one for the polystyrene opal prepared. This finding provides a strong support for, by using polystyrene opal as template, fabricating a photonic crystal with inverse fcc structure of full band gap if the refractive index contrast is higher than 2.8 and the filling fraction of the high index materials is between 0.2 and 0.3.

Microscopy evidence of the face-centered cubic arrangement of monodisperse polystyrene nanospheres

International Nuclear Information System (INIS)

Zhang Hui; Duan Renguan; Li Fan; Tang Qing; Li Wenchao

2007-01-01

This paper reports a scanning electron microscopy (SEM) investigation of polystyrene artificial opal achieved through self-assembly of monodisperse polystyrene nanospheres with a diameter of 250 nm from colloidal suspension after being ambient dried. A detailed analysis of the SEM images verifies that the face-centered cubic (fcc) phase is the most stable one for the polystyrene opal prepared. This finding provides a strong support for, by using polystyrene opal as template, fabricating a photonic crystal with inverse fcc structure of full band gap if the refractive index contrast is higher than 2.8 and the filling fraction of the high index materials is between 0.2 and 0.3

Increased adsorption of histidine-tagged proteins onto tissue culture polystyrene.

Science.gov (United States)

Holmberg, Maria; Hansen, Thomas Steen; Lind, Johan Ulrik; Hjortø, Gertrud Malene

2012-04-01

In this study we compare histidine-tagged and native proteins with regards to adsorption properties. We observe significantly increased adsorption of proteins with an incorporated polyhistidine amino acid motif (HIS-tag) onto tissue culture polystyrene (TCPS) compared to similar proteins without a HIS-tag. The effect is not observed on polystyrene (PS). Adsorption experiments have been performed at physiological pH (7.4) and the effect was only observed for the investigated proteins that have pI values below or around 7.4. Competitive adsorption experiments with imidazole and ethylenediaminetetraacetic acid (EDTA), as well as adsorption performed at different pH and ionic strength indicates that the high adsorption is caused by electrostatic interaction between negatively charged carboxylate groups on the TCPS surface and positively charged histidine residues in the proteins. Pre-adsorption of bovine serum albumin (BSA) does not decrease the adsorption of HIS-tagged proteins onto TCPS. Our findings identify a potential problem in using HIS-tagged signalling molecule in assays with cells cultured on TCPS, since the concentration of the molecule in solution might be affected and this could critically influence the assay outcome. Copyright © 2011 Elsevier B.V. All rights reserved.

Structure and phase behaviour of diblock copolymer monolayers investigated by means of Monte Carlo simulation

International Nuclear Information System (INIS)

Słyk, Edyta; Rżysko, Wojciech; Bryk, Paweł

2015-01-01

We use grand canonical Monte Carlo simulation paired with multiple histogram reweighting, hyperparallel tempering and finite size scaling to investigate the structure and phase behaviour of monolayers of diblock copolymers. The chain molecules are arranged on the square lattice and we consider both fully flexible and rod-coil polymer models. In contrast to the majority of previous studies we assume that the interactions between the segments belonging to one of the two subunits are weaker than the remaining segment–segment interactions. We find that when the diblock copolymer is fully flexible, this choice of the interactions leads to a suppression of the ordered phase, and the phase behaviour is analogous to that of the fully flexible homopolymer model. However, when one of the subunits is rigid, we observe the formation of a novel hairpin chessboard ordered structure with fully stretched chains bent in the middle. The topology of the phase diagram depends on the chain length. For shorter chains the global phase diagram features a critical point and a triple point. For longer chains the gas—disordered liquid phase transition is suppressed and only the order–disorder transition remains stable. The resulting phase diagram is of the swan neck type. (paper)

Mortar modified with sulfonated polystyrene produced from waste plastic cups

Directory of Open Access Journals (Sweden)

L. A. C. MOTTA

Full Text Available Abstract In this work, we studied the addition of sulfonated polystyrene produced from waste plastic cups as an admixture for mortars. Mortars were analyzed with polystyrene content of 0.0; 0.2; 0.6; 1.0 and 1.4% in relation to the cement mass. The influence of polystyrene on the mortars' properties was evaluated by the consistency index, water retention, water absorption, porosity, elasticity modulus, compressive strength, flexural strength, bond tensile strength and microscopy. The increase in the sulfonated polystyrene content decreased the elasticity modulus of the mortar and, despite higher porosity, there was a reduction of water absorption by capillarity. In relation to mortar without admixture, the modified mortar showed an increase in water retention and consistency index, and a large increase in flexural strength and bond tensile strength. The significant increase of bond tensile strength (214% with admixture 1% highlights the potential of the produced material as an adhesive mortar.

Evaluation of Biaxial Mechanical Properties of Aortic Media Based on the Lamellar Microstructure

Directory of Open Access Journals (Sweden)

Hadi Taghizadeh

2015-01-01

Full Text Available Evaluation of the mechanical properties of arterial wall components is necessary for establishing a precise mechanical model applicable in various physiological and pathological conditions, such as remodeling. In this contribution, a new approach for the evaluation of the mechanical properties of aortic media accounting for the lamellar structure is proposed. We assumed aortic media to be composed of two sets of concentric layers, namely sheets of elastin (Layer I and interstitial layers composed of mostly collagen bundles, fine elastic fibers and smooth muscle cells (Layer II. Biaxial mechanical tests were carried out on human thoracic aortic samples, and histological staining was performed to distinguish wall lamellae for determining the dimensions of the layers. A neo-Hookean strain energy function (SEF for Layer I and a four-parameter exponential SEF for Layer II were allocated. Nonlinear regression was used to find the material parameters of the proposed microstructural model based on experimental data. The non-linear behavior of media layers confirmed the higher contribution of elastic tissue in lower strains and the gradual engagement of collagen fibers. The resulting model determines the nonlinear anisotropic behavior of aortic media through the lamellar microstructure and can be assistive in the study of wall remodeling due to alterations in lamellar structure during pathological conditions and aging.

On the mechanism of crack propagation resistance of fully lamellar TiAl alloy

International Nuclear Information System (INIS)

Cao, R.; Yao, H.J.; Chen, J.H.; Zhang, J.

2006-01-01

The study was done using notched two-colony thick tensile specimens of a directionally solidified cast fully lamellar TiAl alloy. In-situ observations of fracture processes in scanning electron microscope (SEM) were combined with section-to-section related observations of fracture surfaces to investigate the crack growth process. Finite element method (FEM) calculations are carried out to evaluate the stresses for propagating cracks. The results reveal that: (1) the reason why enhancement of applied load is required to propagate the main crack, was attributed to that the main crack observed at the surface did not extend all the way through the specimen's thickness thus the stress field was still controlled by the notch, in which a definite stress required for extending a crack tip should be kept by increasing the applied load. (2) Crack propagation resistance is enhanced at colony boundaries, only when a change occurs from an inter-lamellar propagation to a trans-lamellar propagation (3) Ligament bridging toughening phenomena can be integrated into aforementioned mechanism. As a whole the processes of new crack nucleation with bridging ligament formation decreases the crack propagation resistance rather than increasing it. (4) In case the majority of microcracks are surface cracks, the effect of microcrack shielding is not obvious

Mechanical contribution of lamellar and interlamellar elastin along the mouse aorta.

Science.gov (United States)

Clark, T E; Lillie, M A; Vogl, A W; Gosline, J M; Shadwick, R E

2015-10-15

The mechanical properties of aortic elastin vary regionally, but the microstructural basis for this variation is unknown. This study was designed to identify the relative contributions of lamellar and interlamellar elastin to circumferential load bearing in the mouse thoracic and abdominal aortas. Forces developed in uniaxial tests of samples of fresh and autoclaved aorta were correlated with elastin content and morphology obtained from histology and multiphoton laser scanning microscopy. Autoclaving should render much of the interlamellar elastin mechanically incompetent. In autoclaved tissue force per unit sample width correlated with lamellar elastin content (P≪0.001) but not total elastin content. In fresh tissue at low strain where elastin dominates the mechanical response, forces were higher than in the autoclaved tissue, but force did not correlate with total elastin content. Therefore although interlamellar elastin likely contributed to the stiffness in the fresh aorta, its contribution appeared not in proportion to its quantity. In both fresh and autoclaved tissue, elastin stiffness consistently decreased along the abdominal aorta, a key area for aneurysm development, and this difference could not be fully accounted for on the basis of either lamellar or total elastin content. These findings are relevant to the development of mathematical models of arterial mechanics, particularly for mouse models of arterial diseases involving elastic tissue. In microstructural based models the quantity of each mural constituent determines its contribution to the total response. This study shows elastin's mechanical response cannot necessarily be accounted for on the basis of fibre quantity, orientation, and modulus. Copyright © 2015 Elsevier Ltd. All rights reserved.

Radiation-induced chemical processes in polystyrene scintillators

International Nuclear Information System (INIS)

Milinchuk, V.K.; Bolbit, N.M.; Klinshpont, E.R.; Tupikov, V.I.; Zhdanov, G.S.; Taraban, S.B.; Shelukhov, I.P.; Smoljanskii, A.S.

1999-01-01

The regularities established for macroradical accumulation and intensity of radioluminescence under γ-irradiation of a polystyrene scintillator prove benzyl macroradicals to be efficient quenchers of the excited scintillator molecules. Dissolved oxygen was determined to have a constant of the quenching rate 100 times lower than that of macroradicals. Oxygen is an efficient antirad because of participating in oxidation reactions and subsequent recombination of macroradicals. The method was developed to obtain a polymeric scintillator with a polystyrene matrix containing a dispersed system of pores and channels. Radiation resistance of such a scintillator is 5-10 times higher than that of standard types

RESEARCHES OF WORKING LIFE OF FOAM POLYSTYRENE OF BUILDING APPOINTMENT

Directory of Open Access Journals (Sweden)

Guyumdzhjan Perch Pogosovich

2012-09-01

Full Text Available Results of experimental researches of physicomechanical properties of foam polystyrene thermal insulation materials are presented in article. The operational resource was defined on materials subject to ageing, action of liquid excited environments and atmospheric impacts. The destructive processes leading to destruction of foam polystyrene are revealed.

Atmospheric pressure plasma polymerization of 1,3-butadiene for hydrophobic finishing of textile substrates

International Nuclear Information System (INIS)

Samanta, Kartick K; Jassal, Manjeet; Agrawal, Ashwini K

2010-01-01

Atmospheric pressure plasma processing of textile has both ecological and economical advantages over the wet-chemical processing. However, reaction in atmospheric pressure plasma has important challenges to be overcome before it can be successfully used for finishing applications in textile. These challenges are (i) generating stable glow plasma in presence liquid/gaseous monomer, and (ii) keeping the generated radicals active in the presence of contaminants such as oxygen and air. In this study, a stable glow plasma was generated at atmospheric pressure in the mixture of gaseous reactive monomer-1,3-butadiene and He and was made to react with cellulosic textile substrate. After 12 min of plasma treatment, the hydrophilic surface of the cellulosic substrate turned into highly hydrophobic surface. The hydrophobic finish was found to be durable to soap washing. After soap washing, a water drop of 37 μl took around 250 s to get absorbed in the treated sample compared to 0 . Both top and bottom sides of the fabric showed similar hydrophobic results in terms of water absorbency and contact angle. The results may be attributed to chemical reaction of butadiene with the cellulosic textile substrate. The surface characterization of the plasma modified samples under SEM and AFM revealed modification of the surface under <100 nm. The results showed that atmospheric pressure plasma can be successfully used for carrying out reaction of 1,3-butadiene with cellulosic textile substrates for producing hydrophobic surface finish.

SYNTHESIS AND PHARMACOLOGICAL EFFECTS OF BUTADIENE AND CYCLOPENTADIENE ADDUCTS OF METHANDROSTENOLONE IN RATS

Directory of Open Access Journals (Sweden)

FAZEL SHAMSA

2006-06-01

Full Text Available In this study the reactivity of methandrostenolone or [(17b-17-hydroxy-17-methylandrosta-1, 4-diene-3-one], as a dienophil in a Diels-Alder type cycloaddition reaction was investigated. The purpose of this approach was to investigate whether the 1-dehydro position of methandrostenolone 1 undergoes a cycloaddition reaction with dienes, such as 1, 3 butadiene or cyclopentadiene, and to investigate the biological behavior of the reaction adducts, i.e, compound 3 {(17b-17-hydroxy-17-methyl androsta [1a, 2a] cyclohex 3’, 4-diene-3-one} and compound 4 {(17b-17-hydroxy-17-methyl androsta [1a, 2a] cyclohex (2’,5’ methylene 3’, 4-diene-3-one}, relative to compound 1. The results indicated that thedDiels-Alder reactionddid notpproceed under the usual circumstances of high pressure and temperature, but could proceed in the presence of a Lewis acid (AlCl3. The structures of compounds 3 and 4 were confirmed by spectroscopic methods. The androgenic behavior of compounds 3 and 4 in comparison to compound 1 in the apomorphine test indicated that both compounds were almost devoid of androgenic activity, but prevented apomorphine mediated penile erection in male rats in a similar manner as cyproterone acetate.

How the Complex Interplay between Different Blocks Determines the Isothermal Crystallization Kinetics of Triple-Crystalline PEO-b-PCL-b-PLLA Triblock Terpolymers

KAUST Repository

Palacios, Jordana K.

2017-12-05

PEO-b-PCL-b-PLLA triblock terpolymers are fascinating triple-crystalline materials. In this work, the isothermal crystallization kinetics of these terpolymers evaluated by differential scanning calorimetry (DSC) is presented for the first time and compared to analogous PCL-b-PLLA diblock copolymers and to PLLA, PCL, and PEO homopolymers. The results are complemented by in situ SAXS/WAXS synchrotron experiments. One-, two-, and three-step crystallization protocols were employed to study the crystallization kinetics of the blocks. At PLLA block crystallization temperatures, both PCL and PEO molten chains caused a strong plasticizing effect on the PLLA block crystallization, and the overall crystallization rate of the PLLA block in the terpolymers was higher than that in the PLLA-b-PCL diblock copolymers. In the case of the PCL block, the crystallization was followed after PLLA was fully crystallized (two-step crystallization). A nucleating effect induced by the previously formed PLLA crystals was observed. However, an antiplasticizing effect on PCL crystallization was detected if the sample is quenched directly from the melt to the PCL crystallization temperature (one-step crystallization). Finally, the crystallization of the PEO block was followed after PLLA and PCL had fully crystallized (three-step crystallization). The PEO crystallization rate highly decreased due to the confinement imposed by the previously formed PLLA and PCL crystals. Complex competitive effects such as plasticization, nucleation, antiplasticization, and confinement occurred during the isothermal crystallization of tricrystalline PEO-b-PCL-b-PLLA triblock terpolymers.

How the Complex Interplay between Different Blocks Determines the Isothermal Crystallization Kinetics of Triple-Crystalline PEO-b-PCL-b-PLLA Triblock Terpolymers

KAUST Repository

Palacios, Jordana K.; Zhao, Junpeng; Hadjichristidis, Nikolaos; Mü ller, Alejandro J.

2017-01-01

PEO-b-PCL-b-PLLA triblock terpolymers are fascinating triple-crystalline materials. In this work, the isothermal crystallization kinetics of these terpolymers evaluated by differential scanning calorimetry (DSC) is presented for the first time and compared to analogous PCL-b-PLLA diblock copolymers and to PLLA, PCL, and PEO homopolymers. The results are complemented by in situ SAXS/WAXS synchrotron experiments. One-, two-, and three-step crystallization protocols were employed to study the crystallization kinetics of the blocks. At PLLA block crystallization temperatures, both PCL and PEO molten chains caused a strong plasticizing effect on the PLLA block crystallization, and the overall crystallization rate of the PLLA block in the terpolymers was higher than that in the PLLA-b-PCL diblock copolymers. In the case of the PCL block, the crystallization was followed after PLLA was fully crystallized (two-step crystallization). A nucleating effect induced by the previously formed PLLA crystals was observed. However, an antiplasticizing effect on PCL crystallization was detected if the sample is quenched directly from the melt to the PCL crystallization temperature (one-step crystallization). Finally, the crystallization of the PEO block was followed after PLLA and PCL had fully crystallized (three-step crystallization). The PEO crystallization rate highly decreased due to the confinement imposed by the previously formed PLLA and PCL crystals. Complex competitive effects such as plasticization, nucleation, antiplasticization, and confinement occurred during the isothermal crystallization of tricrystalline PEO-b-PCL-b-PLLA triblock terpolymers.

Characterization of SWNT based Polystyrene Nanocomposites

Science.gov (United States)

Mitchell, Cynthia; Bahr, Jeffrey; Tour, James; Arepalli, Sivaram; Krishnamoorti, Ramanan

2003-03-01

Polystyrene nanocomposites with functionalized single walled carbon nanotubes (SWNTs), prepared by the in-situ generation and addition of organic diazonium compounds, were characterized using a range of structural and dynamic methods. These were contrasted to the properties of polystyrene composites prepared with unfunctionalized SWNTs at the same loadings. The functionalized nanocomposites demonstrated a percolated SWNT network structure at concentrations of 1 vol SWNT based composites at similar loadings of SWNT exhibited behavior comparable to that of the unfilled polymer. This formation of the SWNT network structure is because of the improved compatibility between the SWNTs and the polymer matrix due to the functionalization. Further structural evidence for the compatibility of the modified SWNTs and the polymer matrix will be discussed in the presentation.

A UniChem and electron momentum spectroscopy investigations into the valence electronic structure of trans 1,3 butadiene

International Nuclear Information System (INIS)

Michalewicz, M.T.; Winkler, D.A.; Brunger, M.J.; McCarthy, L.E.; Von Niessen, W.

1996-09-01

The experimental (e,2e) coincidence spectroscopy, known as electron momentum spectroscopy (EMS) was applied to the trans 1,3 butadiene (C 4 H 6 ) molecule with detailed binding energy spectra and orbital momentum distributions (MDs) being measured. A small selection of this data is presented. The usage of UniChem computational chemistry codes for the Flinders-developed AMOLD program allows to calculate theoretical MDs for each orbital, to help elucidate the valence electronic structure of butadiene. The results of the many-body Green's function calculation is also presented, to the ADC(3) level, for the binding energies and spectroscopic factors of the respective orbitals of C 4 H 6 . A critical comparison between the experimental and theoretical MDs allows to determine the optimum wavefunction from the basis sets studied. The determination of the wavefunction then allows to make further use of the UniChem package to derive butadiene's chemically interesting molecular properties. A summary of these results and comparison of them with the previous results of other workers is presented. 23 refs., 2 tabs., 2 figs

Seeded emulsion polymerization of butadiene. 2. Effects of persulfate and tert-dodecyl mercaptan

NARCIS (Netherlands)

Verdurmen, E.M.F.J.; Geurts, J.M.; Verstegen, J.M.; Maxwell, I.A.; German, A.L.

1993-01-01

The kinetics of the emulsion polymn. of butadiene at 60 Deg in Smith-Ewart interval III were investigated using sodium persulfate as initiator. Monomer conversion was based on gravimetrically calibrated online densitometry. Plots of the product of the propagation rate coeff., Kp, and the av. no. of

Biomarkers in Czech workers exposed to 1,3-butadiene: a transitional epidemiologic study

NARCIS (Netherlands)

Albertini, Richard J.; Srám, Radim J.; Vacek, Pamela M.; Lynch, Jeremiah; Nicklas, Janice A.; van Sittert, Nico J.; Boogaard, Peter J.; Henderson, Rogene F.; Swenberg, James A.; Tates, Ad D.; Ward, Jonathan B.; Wright, Michael; Ammenheuser, Marinel M.; Binkova, Blanka; Blackwell, Walter; de Zwart, Franz A.; Krako, Dean; Krone, Jennifer; Megens, Hendricus; Musilová, Petra; Rajská, Gabriela; Ranasinghe, Asoka; Rosenblatt, Judah I.; Rössner, Pavel; Rubes, Jiri; Sullivan, Linda; Upton, Patricia; Zwinderman, Ailko H.

2003-01-01

A multiinstitutional, transitional epidemiologic study was conducted with a worker population in the Czech Republic to evaluate the utility of a continuum of non-disease biological responses as biomarkers of exposure to 1,3-butadiene (BD)* in an industrial setting. The study site included two BD

Fabrication and characterization of large size 6LiF/CaF2:Eu eutectic composites with the ordered lamellar structure

International Nuclear Information System (INIS)

Kawaguchi, Noriaki; Fukuda, Kentaro; Yanagida, Takayuki; Fujimoto, Yutaka; Yokota, Yuui; Suyama, Toshihisa; Watanabe, Kenichi; Yamazaki, Atsushi; Yoshikawa, Akira

2011-01-01

As alternative candidates for the 3 He neutron detectors, 6 LiF/CaF 2 :Eu eutectic composites were fabricated and their scintillation properties were evaluated. Large size LiF/CaF 2 :Eu eutectic composites of 58 mm diameter and 50 mm thickness were produced by Bridgman method. The composites had a finely ordered lamellar structure along the solidification direction. The lamellar structure was controlled by the direction and the rate of solidification, and it was optimized to improve the scintillation properties. Better results were achieved when thinner lamellar layers were aligned along the scintillation light path.

Study of crystalline morphology and phase structure in poly(styrene-b-ethylene oxide-b-styrene) triblock copolymers bu solid state RMN spin diffusion

International Nuclear Information System (INIS)

Mantovani, Gerson L.; Phan, Trang; Bertin, Denis; Azevedo, Eduardo R. de; Bonagamba, Tito J.

2009-01-01

The phase structure and crystalline morphology of a series of polystyrene-b-polyethylene oxide-b-polystyrene (PS-b- PEO-b-PS) triblock copolymers, with different compositions and molecular weights, has been studied by solid-state NMR. WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethylene oxide (PEO) blocks at room temperature as a function of the copolymer composition. 1 H NMR spin diffusion analyses provided an estimation of the size of the dispersed phases of the nano structured copolymers. (author)

Preparation of tritiated polystyrene and its application in radio luminescent paints

International Nuclear Information System (INIS)

Ravi, S.; Mathewy, K.M.; Seshadri, N.K.; Subramanian, T.K.

2001-01-01

Beta radiation emanating from tritiated polystyrene in close proximity with copper activated zinc sulphide phosphor will provide self-sustained light sources and are used for nocturnal illumination of watches and clocks, product advertisements, telephone numbers, exit signs etc. Phenylacetylene was partially reduced in diethyl ether medium with tritium using 5% Pd/C poisoned with quinoline to give styrene. Styrene formed was polymerised to polystyrene by subjecting it to irradiation with γ-radiation (20 mega rad dose). Copper activated zinc sulphide phosphor was coated with tritiated polystyrene to give self-sustained light sources. (author)

Personal exposure to benzene and 1,3-butadiene during petroleum refinery turnarounds and work in the oil harbour.

Science.gov (United States)

Akerstrom, M; Almerud, P; Andersson, E M; Strandberg, B; Sallsten, G

2016-11-01

Petroleum refinery workers' exposure to the carcinogens benzene and 1,3-butadiene has decreased during normal operations. However, certain occupational groups or events at the refineries still involve a risk of higher exposures. The aim of this study was to examine the personal exposure to benzene and 1,3-butadiene at refinery turnarounds and during work in the oil harbour. Personal exposure measurements of benzene and 1,3-butadiene were taken during work shifts, with a priori assumed higher benzene exposure, using PerkinElmer diffusive samplers filled with Carbopack X. Mean exposure levels were calculated, and repeated exposure measurements, when available, were assessed using mixed effect models. Group and individual compliance with the Swedish occupational exposure limit (OEL) was tested for the different exposure groups. Mean benzene exposure levels for refinery workers during the three measured turnarounds were 150, 610 and 960 µg/m 3 , and mean exposures for oil harbour workers and sewage tanker drivers were 310 and 360 µg/m 3 , respectively. Higher exposures were associated with handling benzene-rich products. Most occupational groups did not comply with the Swedish OEL for benzene nor did the individuals within the groups. The exposure to 1,3-butadiene was very low, between Work within the petroleum refinery industry, with potential exposure to open product streams containing higher fractions of benzene, pose a risk of personal benzene exposures exceeding the OEL. Refinery workers performing these work tasks frequently, such as contractors, sewage tanker drivers and oil harbour workers, need to be identified and protected.

Influence of gamma radiation on the crosslinking properties of oligo-butadiene-base polyurethane elastomers

International Nuclear Information System (INIS)

Dedgaonkar, V.G.

1994-01-01

Liquid oligo-butadiene-base diol was cured by gammas when a diisocyanate and a triol were present. The NCO/OH ratio was at unity. Radiation brought about crosslink networks through urethane linkages and among polybutadiene segments. (author). 5 refs., 1 tab

A Molecular Simulation Approach to the Prediction of the Morphology of Self-Assembled Nanoparticles in Diblock Copolymers

Czech Academy of Sciences Publication Activity Database

Posocco, P.; Posel, Z.; Fermeglia, M.; Lísal, Martin; Pricl, S.

2010-01-01

Roč. 20, č. 46 (2010), s. 10511-10520 ISSN 0959-9428 R&D Projects: GA ČR GA203/08/0094; GA AV ČR KAN400720701 Grant - others:EC(XE) TD0802/OC10053 Institutional research plan: CEZ:AV0Z40720504 Keywords : diblock copolymers * nanoparticles * computer simulation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.101, year: 2010

Investigation of Universal Behavior in Symmetric Diblock Copolymer Melts

Science.gov (United States)

Medapuram, Pavani

the effective interaction parameter chie upon the strength of the AB repulsion. The results show that behavior near the ODT exhibits a different character at moderate and high values of N¯, with a crossover near N¯ ≃ 104. Within the range N¯ ≤sssim 104 studied in this work, the ordered and disordered phases near the ODT both contain strongly segregated domains of nearly pure A and B, in contrast to the assumption of weak segregation underlying the Fredrickson-Helfand (FH) theory. In this regime, the FH theory is inaccurate and substantially underestimates the value of chieN at the ODT. Results for the highest values of N¯ studied here agree reasonably well with FH predictions, suggesting that the theory may be accurate for N¯ gtrsim 104. Self-consistent field theory (SCFT) grossly underestimates (chieN)ODT for modest N¯ because it cannot describe strong correlations in the disordered phase. SCFT is found, however, to yield accurate predictions for several properties of the ordered lamellar phase. A detailed quantitative comparison of experimental results to theoretical predictions and obtained simulations results is also presented. Experimental results for structure factor obtained from small-angle neutron and X-ray scattering (SANS and SAXS) measurements are analyzed using methods closely analogous to those used to analyze simulation results. Peak scattering intensity results of different chain lengths of a AB pair are fitted to the ROL theory predictions in order to estimate the effective interaction parameter chi e(T) of the chemical system. The resulting chi e(T) estimates are used to obtain ODT values (chieN)ODT of different experimental systems, which we compare to the scaling law obtained from simulation results and to theoretical predictions. The results are largely consistent with the expected systematic decrease with increasing N¯ and lie closer to the simulations scaling law than to any theoretical prediction. These results confirm the

Durability and Performance of Polystyrene-b-Poly(vinylbenzyl trimethylammonium) Diblock Copolymer and Equivalent Blend Anion Exchange Membranes

Science.gov (United States)

2015-01-01

requiring circulation of the electrolyte to filter out the carbonate solids. The superior power density of proton exchange membrane fuel cells ( PEMFC ...without requir- ing a CO2 free oxidant stream, prevented commercial develop- ment of the liquid AFC, allowing PEMFCs to dominate low temperature fuel...cell research and development. PEMFCs employ a solid acidic polymer to transport protons from anode to cathode. PEMs have been researched heavily the

Small angle neutron scattering study on star di-block copolymers

International Nuclear Information System (INIS)

Ertugrul, O.

2006-01-01

Determining structural properties, phase transitions and stability of polymer mixtures is very important to produce new materials with desired and interesting properties. Small Angle Neutron Scattering Technique (SANS) has been one of the most powerful and intensely used methods for the characterization of polymers for last decades, m this study, we use a model based on Gaussian Random Phase Approximation (RPA) to describe Star Di-block Copolymers (SDC) mixtures with homo-polymers. We could able to predict the miscibility and phase transitions of the various mixtures along with their structure factors, producing a thermodynamic picture of the system. Also the results suggest that scattering intensity will be dictated by the structure factor of the core or shell parts of star polymer only, which depends on the homo-polymer type of the mixture

Evaluation of Recycling Polystyrene (PS) from a Microbiology Product

OpenAIRE

Eklöf, Jonas

2014-01-01

Detta är ett beställningsarbete av Plastone Oy och i det undersöks möjligheterna vad man kan göra genom återvinning med avfallsmaterialet som uppstår då man tillverkar en mikrobiologisk produkt i deras plastfabrik. Produkten tillverkas genom formsprutning och materialet som används är polystyren (PS). Ur litteraturstudien fann man varierande möjligheter på hur man kan återvinna PS på bästa sätt, men ingen lösning som har varit effektiv i praktiken. Det framgick också att återvunnet PS inte är...

Growth crystallography and lamellar to rod transition in directionally solidified Nb--Nb2C eutectic composites

International Nuclear Information System (INIS)

David, S.A.; Santhanam, A.T.; Brody, H.D.

1976-01-01

The transition in morphology of the carbide phase is discussed in terms of the relative volume fraction of the phases, growth rate, and orientation relationships. The carbide morphology is influenced by the growth rate and carbon content. For constant growth rate increasing the volume fraction of the carbide phase favors the lamellar morphology. At low growth rates the lamellar morphology is favored, and at high growth rates the rod-like morphology is favored. Growth crystallography has no direct influence on the transition in carbide morphology

Nanostructured Double Hydrophobic Poly(Styrene-b-Methyl Methacrylate) Block Copolymer Membrane Manufactured Via Phase Inversion Technique

KAUST Repository

Karunakaran, Madhavan; Shevate, Rahul; Peinemann, Klaus-Viktor

2016-01-01

In this paper, we demonstrate the formation of nanostructured double hydrophobic poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer membranes via state-of-the-art phase inversion technique. The nanostructured membrane morphologies are tuned by different solvent and block copolymer compositions. The membrane morphology has been investigated using FESEM, AFM and TEM. Morphological investigation shows the formation of both cylindrical and lamellar structures on the top surface of the block copolymer membranes. The PS-b-PMMA having an equal block length (PS160K-b-PMMA160K) exhibits both cylindrical and lamellar structures on the top layer of the asymmetric membrane. All membranes fabricated from PS160K-b-PMMA160K shows an incomplete pore formation in both cylindrical and lamellar morphologies during the phase inversion process. However, PS-b-PMMA (PS135K-b-PMMA19.5K) block copolymer having a short PMMA block allowed us to produce open pore structures with ordered hexagonal cylindrical pores during the phase inversion process. The resulting PS-b-PMMA nanostructured block copolymer membranes have pure water flux from 105-820 l/m2.h.bar and 95% retention of PEG50K

Nanostructured Double Hydrophobic Poly(Styrene-b-Methyl Methacrylate) Block Copolymer Membrane Manufactured Via Phase Inversion Technique

KAUST Repository

Karunakaran, Madhavan

2016-03-11

In this paper, we demonstrate the formation of nanostructured double hydrophobic poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer membranes via state-of-the-art phase inversion technique. The nanostructured membrane morphologies are tuned by different solvent and block copolymer compositions. The membrane morphology has been investigated using FESEM, AFM and TEM. Morphological investigation shows the formation of both cylindrical and lamellar structures on the top surface of the block copolymer membranes. The PS-b-PMMA having an equal block length (PS160K-b-PMMA160K) exhibits both cylindrical and lamellar structures on the top layer of the asymmetric membrane. All membranes fabricated from PS160K-b-PMMA160K shows an incomplete pore formation in both cylindrical and lamellar morphologies during the phase inversion process. However, PS-b-PMMA (PS135K-b-PMMA19.5K) block copolymer having a short PMMA block allowed us to produce open pore structures with ordered hexagonal cylindrical pores during the phase inversion process. The resulting PS-b-PMMA nanostructured block copolymer membranes have pure water flux from 105-820 l/m2.h.bar and 95% retention of PEG50K

Structural analysis of syndiotactic polystyrene

Energy Technology Data Exchange (ETDEWEB)

Mitani, Masahiro

1988-09-01

Since the stereostructure of a high-molecular compound includes three types of isotactic, atactic and sydiotactic structures, a high-molecular compound with excellent properties can be produced by controlling the stereogularity of the compound with the identical composition. The stereoregularity of a stereogular polystyrene, or syndiotactic polystyrene (SPS), which had been successfully synthesized recently was quantitatively determined and the open chain structure by polymerization was investigated by nuclear magnetic resonance spectroscopy. Two SPSs were synthesized from cis-beta-d/sub/1-styrene and trans-beta-d/sub/1-styrene with alpha, beta, beta-d/sub/3-styrene. The results of spectral analysis of these two SPSs indicate that the former is of trans-conformation and the latter is of gauche conformation and that accordingly the open chain structure by polymerization of SPS is of cis-open chain and SPS has a planar zigzag structure even in the solution. (5 figs, 9 refs)

Analytic theory of soft x-ray diffraction by lamellar multilayer gratings

NARCIS (Netherlands)

Kozhevnikov, I.V.; van der Meer, R.; Bastiaens, Hubertus M.J.; Boller, Klaus J.; Bijkerk, Frederik

2011-01-01

An analytic theory describing soft x-ray diffraction by Lamellar Multilayer Gratings (LMG) has been developed. The theory is derived from a coupled waves approach for LMGs operating in the single-order regime, where an incident plane wave can only excite a single diffraction order. The results from

Inverse cutting of posterior lamellar corneal grafts by a femtosecond laser

DEFF Research Database (Denmark)

Hjortdal, Jesper; Nielsen, Esben; Vestergaard, Anders Højslet

2012-01-01

(range: 1.400 to 2.000 cells per sq. mm). The grafts were of uniform thickness, but substantial interface haze was present in most grafts. Conclusions: Posterior lamellar corneal grafts can be prepared from the endothelial side using a femto-second laser. All grafts were clear after 6 months...

Facile approach in fabricating superhydrophobic ZnO/polystyrene nanocomposite coating

Science.gov (United States)

Qing, Yongquan; Zheng, Yansheng; Hu, Chuanbo; Wang, Yong; He, Yi; Gong, Yong; Mo, Qian

2013-11-01

In this paper, we report a simple and inexpensive method for fabricating modified-ZnO/polystyrene superhydrophobic surface on the cotton textiles. The surface wettability and topology of coating were characterized by contact angle measurement, Scanning electron microscope and Fourier transform infrared spectrometry. The results showed that the hydrophobic CH3 and CF2 group was introduced into ZnO particles via modification, the ZnO nanoparticles were modified from hydrophilic to hydrophobic. When the weight ratio of modified-ZnO to polystyrene was 7:3, the ZnO/polystyrene composite coating contact angle was 158°, coating surface with hierarchical micro/nano structures. Furthermore, the superhydrophobic cotton texiles have a very extensive application prospect in water-oil separation.

Fabrication of polystyrene microfluidic devices using a pulsed CO2 laser system

KAUST Repository

Li, Huawei

2013-10-10

In this article, we described a simple and rapid method for fabrication of droplet microfluidic devices on polystyrene substrate using a CO2 laser system. The effects of the laser power and the cutting speed on the depth, width and aspect ratio of the microchannels fabricated on polystyrene were investigated. The polystyrene microfluidic channels were encapsulated using a hot press bonding technique. The experimental results showed that both discrete droplets and laminar flows could be obtained in the device.

Fabrication of polystyrene microfluidic devices using a pulsed CO2 laser system

KAUST Repository

Li, Huawei; Fan, Yiqiang; Foulds, Ian G.; Kodzius, Rimantas

2013-01-01

In this article, we described a simple and rapid method for fabrication of droplet microfluidic devices on polystyrene substrate using a CO2 laser system. The effects of the laser power and the cutting speed on the depth, width and aspect ratio of the microchannels fabricated on polystyrene were investigated. The polystyrene microfluidic channels were encapsulated using a hot press bonding technique. The experimental results showed that both discrete droplets and laminar flows could be obtained in the device.

Chain elongation suppression of cyclic block copolymers in lamellar microphase-separated bulk

NARCIS (Netherlands)

Matsushita, Y; Iwata, H; Asari, T; Uchida, T; ten Brinke, G; Takano, A

2004-01-01

Chain elongation suppression of cyclic block copolymers in microphase-separated bulk was determined quantitatively. Solvent-cast and annealed films are confirmed to show alternating lamellar structure and their microdomain spacing D increases with increasing total molecular weight M according to the

One-Pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers Via High-Throughput Cu(0-Mediated Polymerization

Directory of Open Access Journals (Sweden)

Lenny Voorhaar

2017-07-01

Full Text Available Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate as a first or middle block and poly(2-(dimethylaminoethyl acrylate, poly(1-ethoxyethyl acrylate and poly(1-ethoxyethyl-2-carboxyethyl acrylate as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylaminoethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.

Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene-block-poly(tert-butyl acrylate) Films

NARCIS (Netherlands)

Duvigneau, Joost; Cornelissen, Stijn; Bardajı´Valls, Nuria; Schönherr, Holger; Vancso, Gyula J.

2009-01-01

Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at