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

DOE PAGES

Misichronis, Konstantinos; Chen, Jihua; Imel, Adam; ...

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 in this paper 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 (T ODT), for the first time formore » PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χ eff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. Finally, 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.« less

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

PubMed

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

Microphase separation of comb copolymers with two different lengths of side chains

NASA Astrophysics Data System (ADS)

Aliev, M. A.; Kuzminyh, N. Yu.

2009-10-01

The phase behavior of the monodisperse AB comb copolymer melt contained the macromolecules of special architecture is discussed. Each macromolecule is assumed to be composed of two comb blocks which differ in numbers of side chains and numbers of monomer units in these chains. It is shown (by analysis of the structure factor of the melt) that microphase separation at two different length scales in the melt is possible. The large and small length scales correspond to separation between comb blocks and separation between monomer units in repeating fragments of blocks, respectively. The classification diagrams indicated which length scale is favored for a given parameters of chemical structure of macromolecules are constructed.

Crystallization and Microphase Separation in Chiral Block Copolymers

NASA Astrophysics Data System (ADS)

Ho, Rong-Ming

2012-02-01

Block copolymers composed of chiral entities, denoted as chiral block copolymers (BCP*s), were designed to fabricate helical architectures from self-assembly. A helical phase (denoted H*) was discovered in the self-assembly of poly(styrene)-b-poly(L-lactide) (PS-PLLA) BCPs*. To examine the phase behavior of the PS-PLLA, self-assembled superstructures resulting from the competition between crystallization and microphase separation of the PS-PLLA in solution were examined. A kinetically controlled process by changing non-solvent addition rate was utilized to control the BCP* self-assembly. Single-crystal lozenge lamellae were obtained by the slow self-assembly (i.e., slow non-solvent addition rate) of PS-PLLA whereas amorphous helical ribbon superstructures were obtained from the fast self-assembly (i.e., fast non-solvent addition rate). As a result, the formation of helical architectures from the self-assembly of the PS-PLLA reflects the impact of chirality on microphase separation, but the chiral effect might be overwhelmed by crystallization. Consequently, various crystalline PS-PLLA nanostructures in bulk were obtained by controlling the crystallization temperature of PLLA (Tc,PLLA) at which crystalline helices and crystalline cylinders occur while Tc,PLLA=x Tg,PS, respectively. Anisotropic arrangement of the PLLA crystallites grown within the microdomains was identified. The formation of this exclusive crystalline growth is attributed to the spatial confinement effect for crystallization. While Tc,PLLA=x Tg,PS, the preferential growth may modulate the curvature of microdomains by shifting the molecular chains to access the fast path for crystalline growth due to the increase in chain mobility. As a result, a spring-like behavior of the helical nanostructure can be driven by crystallization so as to dictate the transformation of helices and to result in crystalline cylinders.

Extremely asymmetric phase diagram of homopolymer-monotethered nanoparticles: Competition between chain conformational entropy and particle steric interaction.

PubMed

Zhang, Tiancai; Fu, Chao; Yang, Yingzi; Qiu, Feng

2017-02-07

The phase behaviors of homopolymer-monotethered nanoparticles (HMNs) in melt are investigated via a theoretical method combining self-consistent field theory for polymers and density functional theory for hard spheres. An extremely asymmetric phase diagram is observed: (i) microphases are only possible for the volume fraction of the tethered polymer f A > 0.35; (ii) in addition to lamellar phase, the system can only self-assemble into various morphologies with a polymer-rich matrix, including gyroid phase, cylindrical phase, and spherical phase. In the frame of this theory, the critical point for HMNs' microphase separation is significantly lower than that of linear diblock copolymers. Furthermore, the characteristic length of microphase-separated structures of HMNs is much smaller than that of linear diblock copolymers with the same molecular weight. Our calculation results on morphologies and characteristic length agree well with recent simulations and experimental observations.

Microphase separation in random multiblock copolymers

NASA Astrophysics Data System (ADS)

Govorun, E. N.; Chertovich, A. V.

2017-01-01

Microphase separation in random multiblock copolymers is studied with the mean-field theory assuming that long blocks of a copolymer are strongly segregated, whereas short blocks are able to penetrate into "alien" domains and exchange between the domains and interfacial layer. A bidisperse copolymer with blocks of only two sizes (long and short) is considered as a model of multiblock copolymers with high polydispersity in the block size. Short blocks of the copolymer play an important role in the microphase separation. First, their penetration into the "alien" domains leads to the formation of joint long blocks in their own domains. Second, short blocks localized at the interface considerably change the interfacial tension. The possibility of penetration of short blocks into the "alien" domains is controlled by the product χ Nsh (χ is the Flory-Huggins interaction parameter and Nsh is the short block length). At not very large χ Nsh , the domain size is larger than that for a regular copolymer consisting of the same long blocks as in the considered random copolymer. At a fixed mean block size, the domain size grows with an increase in the block size dispersity, the rate of the growth being dependent of the more detailed parameters of the block size distribution.

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

PubMed Central

Chavis, Michelle A.; Smilgies, Detlef-M.; Wiesner, Ulrich B.; Ober, Christopher K.

2015-01-01

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, we investigated solvent vapor annealing in supported thin films of poly(2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) [PHEMA-b-PMMA] by means of grazing incidence small angle X–ray scattering (GISAXS). A spin-coated thin film of lamellar block copolymer was solvent vapor annealed to induce microphase separation and improve the long-range order of the self-assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents (methanol, MeOH, and tetrahydrofuran, THF), which are chosen to be preferential for each block, enabled selective formation of ordered lamellae, gyroid, hexagonal or spherical morphologies from a single block copolymer with a fixed volume fraction. The selected microstructure was then kinetically trapped in the dry film by rapid drying. To our knowledge, this paper describes the first reported case where in-situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram. PMID:26819574

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

Larsen, Michael B.; Van Horn, J. David; Wu, Fei

The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. Herein we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trappingmore » of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (Tg) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.« less

A Study on the Kinetics of a Disorder-to-Order Transition Induced by Alkyne/Azide Click Reaction

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

X Wei; L Li; J Kalish

2011-12-31

The kinetics of binary blends of poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) diblock copolymer and Rhodamine B azide was investigated during a disorder-to-order transition induced by alkyne/azide click reaction. The change in the domain spacing and conversion of reactants as a function of annealing time were investigated by in situ small-angle X-ray scattering (SAXS) and infrared spectroscopy (IR), suggesting several kinetic processes with different time scales during thermal annealing. While a higher conversion can be realized by extending the annealing time, the microphase-separated morphology is independent of the annealing conditions, as long as both the reagents and final products have enoughmore » mobility.« less

Ordering transition in salt-doped diblock copolymers

DOE PAGES

Qin, Jian; de Pablo, Juan J.

2016-04-26

Lithium salt-doped block copolymers offer promise for applications as solid electrolytes in lithium ion batteries. Control of the conductivity and mechanical properties of these materials, for membrane applications relies critically on the ability to predict and manipulate their microphase separation temperature. Past attempts to predict the so-called "order-disorder transition temperature" of copolymer electrolytes have relied on approximate treatments of electrostatic interactions. In this work, we introduce a coarse-grained simulation model that treats Coulomb interactions explicitly, and we use it to investigate the ordering transition of charged block copolymers. The order-disorder transition temperature is determined from the ordering free energy, whichmore » we calculate with a high level of precision using a density-of-states approach. Our calculations allow us to discern a delicate competition between two physical effects: ion association, which raises the transition temperature, and solvent dilution, which lowers the transition temperature. Lastly, in the intermediate salt concentration regime, our results predict that the order-disorder transition temperature increases with salt content, in agreement with available experimental data.« less

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

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

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.

Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d 6 azlactone) (PVDMA-d 6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical studymore » reveals that in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d 6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

DOE PAGES

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; ...

2015-02-03

Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this paper, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d 6 azlactone) (PVDMA-d 6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate–monomer and monomer–monomer interactions on the microphase segregation are studied using SCFT. The theoretical studymore » reveals that in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d 6 di-block copolymer deposited on silicon substrates. In conclusion, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers

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

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.

Despite the ubiquity of polydispersity in chain lengths of di-block copolymers, its effects on microphase separation in thin films have eluded a clear understanding. In this work, we have studied effects of polydispersity on the microphase separation in thin films of lamellar forming di-block copolymers using self-consistent field theory (SCFT) and neutron reflectivity experiments. Di-block copolymers containing a polydisperse block of poly(glycidylmethacrylate) (PGMA) connected to a near-monodisperse block poly(2-vinyl-4,4-dimethyl-d6 azlactone) (PVDMA-d6) are considered in this work. Effects of chain length polydispersity, film thickness, substrate-monomer and monomer-monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals thatmore » in comparison to a film created with monodisperse di-block copolymers, an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness. This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index leads to an increase in the effective Kuhn segment length of the polydisperse blocks. It is shown that the conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness decreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. These predictions are verified by results from neutron reflectivity experiments on thin films made from moderately polydisperse PGMA-PVDMA-d6 di-block copolymer deposited on silicon substrates. Finally, results from SCFT are used to predict neutron reflectivity profiles, providing a facile and robust route to obtain useful physical insights into the structure of polydisperse diblock copolymers at interfaces.« less

Disorder-to-order transitions induced by alkyne/azide click chemistry in diblock copolymer thin films.

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

Wei, X.; Gu, W.; Chen, W.

2012-01-01

We investigated thin film morphologies of binary blends of alkyne-functionalized diblock copolymer poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) and Rhodamine B azide, where the thermal alkyne/azide click reaction between the two components induced a disorder-to-order transition (DOT) of the copolymer. By controlling the composition of the neat copolymers and the mole ratio between the alkyne and azide groups, different microphase separated morphologies were achieved. At higher azide loading ratios, a perpendicular orientation of the microdomains was observed with wide accessible film thickness window. As less azide was incorporated, the microdomains have a stronger tendency to be parallel to the substrate, andmore » the film thickness window for perpendicular orientation also became narrower.« less

Binary Polymer Brushes of Strongly Immiscible Polymers.

PubMed

Chu, Elza; Babar, Tashnia; Bruist, Michael F; Sidorenko, Alexander

2015-06-17

The phenomenon of microphase separation is an example of self-assembly in soft matter and has been observed in block copolymers (BCPs) and similar materials (i.e., supramolecular assemblies (SMAs) and homo/block copolymer blends (HBCs)). In this study, we use microphase separation to construct responsive polymer brushes that collapse to generate periodic surfaces. This is achieved by a chemical reaction between the minor block (10%, poly(4-vinylpyridine)) of the block copolymer and a substrate. The major block of polystyrene (PS) forms mosaic-like arrays of grafted patches that are 10-20 nm in size. Depending on the nature of the assembly (SMA, HBC, or neat BCP) and annealing method (exposure to vapors of different solvents or heating above the glass transition temperature), a range of "mosaic" brushes with different parameters can be obtained. Successive grafting of a secondary polymer (polyacrylamide, PAAm) results in the fabrication of binary polymer brushes (BPBs). Upon being exposed to specific selective solvents, BPBs may adopt different conformations. The surface tension and adhesion of the binary brush are governed by the polymer occupying the top stratum. The "mosaic" brush approach allows for a combination of strongly immiscible polymers in one brush. This facilitates substantial contrast in the surface properties upon switching, previously only possible for substrates composed of predetermined nanostructures. We also demonstrate a possible application of such PS/PAAm brushes in a tunable bioadhesion-bioadhesive (PS on top) or nonbioadhesive (PAAm on top) surface as revealed by Escherichia coli bacterial seeding.

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

PubMed

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

2018-03-01

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

Chain end distribution of block copolymer in two-dimensional microphase-separated structure studied by scanning near-field optical microscopy.

PubMed

Sekine, Ryojun; Aoki, Hiroyuki; Ito, Shinzaburo

2009-10-01

The chain end distribution of a block copolymer in a two-dimensional microphase-separated structure was studied by scanning near-field optical microscopy (SNOM). In the monolayer of poly(octadecyl methacrylate)-block-poly(isobutyl methacrylate) (PODMA-b-PiBMA), the free end of the PiBMA subchain was directly observed by SNOM, and the spatial distributions of the whole block and the chain end are examined and compared with the convolution of the point spread function of the microscope and distribution function of the model structures. It was found that the chain end distribution of the block copolymer confined in two dimensions has a peak near the domain center, being concentrated in the narrower region, as compared with three-dimensional systems.

New time-resolved micro-photoluminescence spectroscopy of natural and synthetic analogue minerals

NASA Astrophysics Data System (ADS)

Panczer, G.; Ollier, N.; Champagnon, B.; Gaft, M.

2003-04-01

Minerals as well as geomaterials often present light emissions under UV or visible excitations. This property called photoluminescence is due to low concentration impurities such as the rare earths, the transition elements and the lanthanides. The induced color is used for ore prospection but only spectroscopic analyses indicate the nature of the emitted centers. However natural samples contained numerous luminescent centers simultaneously and with regular steady-state measurements (such as in cathodoluminescence) all the emissions are often over lapping. In order to record the contributions of each separate center, it is possible to use time-resolved measurements based on the decay time of the emissions and using pulsed laser excitation. Some characteristic examples will be presented on apatites, zircons as well as gemstones. Geomaterials present as well micro scale heterogeneities (growth zoning, inclusions, devitrification, microphases...). Precise identification and optical effects of such heterogeneities have to be taken into account. To reach the microscale using photo luminescence studies, a microscope has be modified to allowed pulsed laser injection (from UV to visible), beam focus with micro scale resolution on the sample (<10 μm), as well as time resolved collection of micro fluorescence. Such equipment allows now undertaking time-resolved measurements of microphases. Applications on geomaterials will be presented.

Actuators based on polyurethanes with different types of polyol

NASA Astrophysics Data System (ADS)

Lim, Hyun-Ok; Bark, Geong-Mi; Jo, Nam-Ju

2007-07-01

This study dealt with the electrostrictive responses of polyurethane (PU) actuators with different microphase separation structure, which was a promising candidate for a material used in polymer actuators. In order to construct PUs with different higher-order structure, we synthesized PUs with different diols; poly(neopentyl glycol adipate) (PNAD), poly(tetramethylene glycol) (PTMG), and poly(dimethyl siloxnae) (PDMS). Synthesized PU was characterized by FT-IR spectroscopy and GPC. Thermal analysis and mechanical properties of PU films were carried out with DSC and UTM, respectively. And PU actuator was formed in a monomorph type which made by carbon black electrodes on the both surfaces of PU film by spin coating method. Actuation behavior was mainly influenced on microphase separation structure and mechanical property of PU. In result, PU actuator with PNAD, polyester urethane, had the largest field-induced displacement.

Block copolymer templated self-assembly of disk-shaped molecules

NASA Astrophysics Data System (ADS)

Aragones, J. L.; Alexander-Katz, A.

2017-08-01

Stacking of disk-shaped organic molecules is a promising strategy to develop electronic and photovoltaic devices. Here, we investigate the capability of a soft block copolymer matrix that microphase separates into a cylindrical phase to direct the self-assembly of disk-shaped molecules by means of molecular simulations. We show that two disk molecules confined in the cylinder domain experience a depletion force, induced by the polymer chains, which results in the formation of stacks of disks. This entropic interaction and the soft confinement provided by the matrix are both responsible for the structures that can be self-assembled, which include slanted or columnar stacks. In addition, we evidence the transmission of stresses between the different minority domains of the microphase, which results in the establishment of a long-ranged interaction between disk molecules embedded in different domains; this interaction is of the order of the microphase periodicity and may be exploited to direct assembly of disks at larger scales.

Visible-Light Initiated Free-Radical/Cationic Ring-Opening Hybrid Photopolymerization of Methacrylate/Epoxy: Polymerization Kinetics, Crosslinking Structure, and Dynamic Mechanical Properties.

PubMed

Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette

2015-04-01

The effects of polymerization kinetics and chemical miscibility on the crosslinking structure and mechanical properties of polymers cured by visible-light initiated free-radical/cationic ring-opening hybrid photopolymerization are determined. A three-component initiator system is used and the monomer system contains methacrylates and epoxides. The photopolymerization kinetics is monitored in situ by Fourier transform infrared-attenuated total reflectance. The crosslinking structure is studied by modulated differential scanning calorimetry and dynamic mechanical analysis. X-ray microcomputed tomography is used to evaluate microphase separation. The mechanical properties of polymers formed by hybrid formed by free-radical polymerization. These investigations mark the first time that the benefits of the chain transfer reaction between epoxy and hydroxyl groups of methacrylate, on the crosslinking network and microphase separation during hybrid visible-light initiated photopolymerization, have been determined.

Study on tensile properties constitutive model of polyurethane fibers with different isocyanate index

NASA Astrophysics Data System (ADS)

You, Gexin; Liu, Xinsen; Chen, Xiri; Yang, Bo; Zhou, Xiuwen

2018-06-01

In this study, a two-element model consisting of a non-linear spring and a viscous dashpot was proposed to simulate tensile curve of polyurethane fibers. The results showed that the two-element model can simulate the tensile curve of the polyurethane fibers better with a simple and applicable feature compared to the existing three-element model and four-element model. The effects of isocyanate index (R) on the hydrogen bond (H-bond) and the micro-phase separation of polyurethane fibers were investigated by Fourier transform infrared spectroscopy and x-ray pyrometer, respectively. The degree of H-bond and micro-phase separation increased first and then decreased as the R value increased, and gain a maximum at the value of 1.76, which is in good agreement with parameters viscosity coefficient η and the initial modulus c in the model.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Surface morphology diagram for cylinder-forming block copolymer thin films.

PubMed

Zhang, Xiaohua; Berry, Brian C; Yager, Kevin G; Kim, Sangcheol; Jones, Ronald L; Satija, Sushil; Pickel, Deanna L; Douglas, Jack F; Karim, Alamgir

2008-11-25

We investigate the effect of the ordering temperature (T) and film thickness (h(f)) on the surface morphology of flow-coated block copolymer (BCP) films of asymmetric poly(styrene-block-methyl methacrylate). Morphology transitions observed on the ordered film surface by atomic force microscopy (AFM) are associated with a perpendicular to a parallel cylinder BCP microphase orientation transition with respect to the substrate with increasing h(f). "Hybrid" surface patterns for intermediate h(f) between these limiting morphologies are correspondingly interpreted by a coexistence of these two BCP microphase orientations so that two "transitional" h(f) exist for each T. This explanation of our surface patterns is supported by both neutron reflectivity and rotational SANS measurements. The transitional h(f) values as a function of T define upper and lower surface morphology transition lines, h(fu) (T) and h(fl) (T), respectively, and a surface morphology diagram that should be useful in materials fabrication. Surprisingly, the BCP film surface morphology depends on the method of film formation (flow-coated versus spun-cast films) so that nonequilibrium effects are evidently operative. This morphological variability is attributed primarily to the trapping of residual solvent (toluene) within the film (quantified by neutron reflectivity) due to film vitrification while drying. This effect has significant implications for controlling film structure in nanomanufacturing applications based on BCP templates.

Olefinic Thermoplastic Elastomer Gels: Combining Polymer Crystallization and Microphase Separation in a Selective Solvent

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

Armstrong, Daniel P.; Mineart, Kenneth P.; Lee, Byeongdu

Since selectively swollen thermoplastic elastomer gels (TPEGs) afford a wide range of beneficial properties that open new doors to developing elastomer-based technologies, in this study we examine the unique structure-property behavior of TPEGs composed of olefinic block copolymers (OBCs). Unlike their styrenic counterparts typically possessing two chemically different blocks, this class of multiblock copolymers consists of linear polyethylene hard blocks and poly(ethylene-co-α-octene) soft blocks, in which case, microphase separation between the hard and the soft blocks is accompanied by crystallization of the hard blocks. We prepare olefinic TPEGs (OTPEGs) through the incorporation of a primarily aliphatic oil that selectively swellsmore » the soft block and investigate the resultant morphological features through the use of polarized light microscopy and small-/wideangle X-ray scattering. These features are correlated with thermal and mechanical property measurements from calorimetry, rheology, and extensiometry to elucidate the roles of crystallization and self-assembly on gel characteristics and establish useful structure-property relationships.« less

Microphase Separation Controlled Beta Sheet Crystallization Kinetics in Silk Fibroin Protein.

NASA Astrophysics Data System (ADS)

Hu, Xiao; Lu, Qiang; Kaplan, David; Cebe, Peggy

2009-03-01

We investigate the mechanism of isothermal crystallization kinetics of beta-sheet crystals in silk multiblock fibrous proteins. The Avrami analysis kinetic theory, for studies of synthetic polymer crystal growth, is for the first time extended to investigate protein self-assembly in beta-sheet rich Bombyx mori silk fibroin samples, using time-resolved Fourier transform infrared spectroscopy, differential scanning calorimetry and synchrotron real-time wide-angle X-ray scattering. Results indicate formation of beta sheet crystals in silk proteins is different from the 3-D spherulitic crystal growth found in synthetic homopolymers. Observations by scanning electron microscopy support the view that the protein structures vary during the different stages of crystal growth, and show a microphase separation pattern after chymotrypsin enzyme biodegradation. We present a model to explain the crystallization of the multiblock silk fibroin protein, by analogy to synthetic block copolymers. This model could be widely applicable in other proteins with multiblock (i.e., crystallizable and non-crystallizable) domains.

Olefinic Thermoplastic Elastomer Gels: Combining Polymer Crystallization and Microphase Separation in a Selective Solvent

DOE PAGES

Armstrong, Daniel P.; Mineart, Kenneth P.; Lee, Byeongdu; ...

2016-11-01

Since selectively swollen thermoplastic elastomer gels (TPEGs) afford a wide range of beneficial properties that open new doors to developing elastomer-based technologies, in this study we examine the unique structure-property behavior of TPEGs composed of olefinic block copolymers (OBCs). Unlike their styrenic counterparts typically possessing two chemically different blocks, this class of multiblock copolymers consists of linear polyethylene hard blocks and poly(ethylene-co-α-octene) soft blocks, in which case, microphase separation between the hard and the soft blocks is accompanied by crystallization of the hard blocks. We prepare olefinic TPEGs (OTPEGs) through the incorporation of a primarily aliphatic oil that selectively swellsmore » the soft block and investigate the resultant morphological features through the use of polarized light microscopy and small-/wideangle X-ray scattering. These features are correlated with thermal and mechanical property measurements from calorimetry, rheology, and extensiometry to elucidate the roles of crystallization and self-assembly on gel characteristics and establish useful structure-property relationships.« less

Conformation of single block copolymer chain in two-dimensional microphase-separated structure studied by scanning near-field optical microscopy.

PubMed

Sekine, Ryojun; Aoki, Hiroyuki; Ito, Shinzaburo

2009-05-21

The localization and orientation of the symmetric diblock copolymer chain in a quasi-two-dimensional microphase-separated structure were studied by scanning near-field optical microscopy (SNOM). In the monolayer of poly(isobutyl methacrylate)-block-poly(octadecyl methacrylate) (PiBMA-b-PODMA), the individual PiBMA subchains were directly observed by SNOM, and the center of mass (CM) and orientational angle relative to the phase interface were examined at the single chain level. It was found that the position of the CM and the orientation of the PiBMA subchain in the lamellar structure were dependent on the curvature of the PiBMA/PODMA interface. As the interface was bent toward the objective chain, the block chain preferred the CM position closer to the domain center, and the conformation was strongly oriented perpendicularly to the domain interface. With increase of the curvature, the steric hindrance among the block chain increases, resulting in the stretched conformation.

Discovery of a Frank-Kasper [sigma] Phase in Sphere-Forming Block Copolymer Melts

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

Lee, Sangwoo; Bluemle, Michael J.; Bates, Frank S.

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma ({sigma}) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the {sigma} phase in undiluted linear block copolymers (and certain branchedmore » dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.« less

Selective Metallization of Well Aligned PS-b-P2VP Block Copolymers in Thin Films and in Confined Geometries

NASA Astrophysics Data System (ADS)

Sievert, James D.; Watkins, James J.; Russell, Thomas P.

2006-03-01

Well aligned, microphase-separated structures of styrene-2-vinylpyridine block copolymers are being used as templates for macromolecule-metal nanocomposites. These composites are either prepared as thin films or confined in nanoporous aluminum oxide membranes. Under optimal conditions, templates are prepared as thin films or confined nanorods and metallized without disturbing the ordered structure. We have developed a procedure that deposits metal within the polymer using supercritical carbon dioxide-soluble metal precursors. The use of supercritical carbon dioxide allows for selective metallization of the polymer at or below the glass transition, without disrupting the morphology. In addition, similar procedures have been investigated using metal salts and acids. Using these techniques, metals and metal-sulfides including silver, gold, platinum and zinc sulfide have been selectively deposited.

Electrostatic Interactions and Self-Assembly in Polymeric Systems

NASA Astrophysics Data System (ADS)

Dobrynin, Andrey

Electrostatic interactions between macroions play an important role in different areas ranging from materials science to biophysics. They are main driving forces behind layer-by-layer assembly technique that allows self-assembly of multilayer films from synthetic polyelectrolytes, DNA, proteins and nanoparticles. They are responsible for complexation and reversible gelation between polyelectrolytes and proteins. In this talk, using results of the molecular dynamics simulations and analytical calculations, I will demonstrate what effect electrostatic interactions, counterion condensation and polymer solvent affinity have on a collapse of polyelectrolyte chain in a poor solvent conditions for the polymer backbone, on complexations and reversible gelation between polyelectrolytes and polyamholytes (unstructured proteins), on microphase separation transitions in spherical and planar charged brushes, and on a layer-by-layer assembly of charged nanoparticles and linear polyelectrolytes on charged surfaces. NSF DMR-1004576 DMR-1409710.

Phase behavior and transitions of self-assembling nano-structured materials

NASA Astrophysics Data System (ADS)

Duan, Hu

Homologous series of supramolecular nanostructures have been investigated by a combination of transmission electron microscopy (TEM), electron diffraction (ED), thermal polarized optical microscopy and X-ray diffraction (XRD). Materials include amphiphilic oligomers and polymer such as charged complexes, dipeptide dendrons semi-fluorinated dendron and polyethyleneimines. Upon microphase separation, they self-assemble into either cylindrical or spherical shapes, which co-organize into a 2D P6mm hexagonal columnar phase or 3D Pm 3¯ n and Im 3¯ m cubic phases. Correlation between the phase selection and molecular architecture is established accordingly. The order-disorder transition (ODT) is explored by rheometry and rheo-optical microscopy in a model polymeric compound poly(N-[3,4-bis(n-dodecan-1-yloxy)benzoyl]ethyleneimine). Shear alignment of the hexagonal columnar liquid crystalline phase along the velocity direction at low temperature and shear disordering in the vicinity of the ODT were observed. After cessation of shear, transformation back to the stable columnar phase follows a row-nucleation mechanism. The order-order transition process is explored in a monodendron that exhibits a hexagonal columnar and a weakly birefringent mesophase. Polarized DIC microscopy strongly supports an epitaxial relationship between them.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Equilibrium Phase Behavior of the Square-Well Linear Microphase-Forming Model.

PubMed

Zhuang, Yuan; Charbonneau, Patrick

2016-07-07

We have recently developed a simulation approach to calculate the equilibrium phase diagram of particle-based microphase formers. Here, this approach is used to calculate the phase behavior of the square-well linear model for different strengths and ranges of the linear long-range repulsive component. The results are compared with various theoretical predictions for microphase formation. The analysis further allows us to better understand the mechanism for microphase formation in colloidal suspensions.

Hemicellulose block copolymers made from woods for wide-range directed self-assembly lithography enabling wider range of applicable patterning size

NASA Astrophysics Data System (ADS)

Morita, Kazuyo; Yamamoto, Kimiko

2017-03-01

Xylan, one of hemicellulose family, block copolymer was newly developed for wide-range directed self-assembly lithography (DSA). Xylan is higher hydrophilic material because of having many hydroxy groups in one molecule. It means that xylan block copolymer has a possibility of high-chi block copolymer. Generally, DSA is focused on microphase separation for smaller size with high-chi block copolymer and not well known for larger size. In this study, xylan block copolymer was confirmed enabling wider range of patterning size, from smaller size to larger size. The key of xylan block copolymer is a new molecular structure of block copolymer and sugar chain control technology. Sugar content is the important parameter for not only micro-phase separation property but also line edge roughness (LER) and defects. Based on the sugar control technology, wide-range (hp 8.3nm to 26nm L/S and CD 10nm to 51nm hole) DSA patterning was demonstrated. Additionally it was confirmed that xylan block copolymer is suitable for sequential infiltration synthesis (SIS) process.

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

PubMed Central

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

2013-01-01

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

Diblock copolymers of polystyrene- b-poly(1,3-cyclohexadiene) exhibiting unique three-phase microdomain morphologies

DOE PAGES

Misichronis, Konstantinos; Chen, Jihua; Kahk, Jong K.; ...

2016-03-29

Here, the synthesis and molecular characterization of a series of conformationally asymmetric polystyrene-block-poly(1,3-cyclohexadiene) (PS- b-PCHD) diblock copolymers (PCHD: ~90% 1,4 and ~10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ Φ PS ≤ 0.91) was studied by transmission electron microscopy and small-angle X-ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD-1,4)–shell(PCHD-1,2) cylinders in PS matrix and three-phase (PS, PCHD-1,4, PCHD-1,2) four-layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strongmore » dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS- b-PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1564–1572« less

Molecular Dynamics Study of Polystyrene-b-poly(ethylene oxide) Asymmetric Diblock Copolymer Systems.

PubMed

Dobies, M; Makrocka-Rydzyk, M; Jenczyk, J; Jarek, M; Spontak, R J; Jurga, S

2017-09-12

Two polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers differing in molecular mass (49 and 78 kDa) but possessing the same PEO cylindrical morphology are examined to elucidate their molecular dynamics. Of particular interest here is the molecular motion of the PEO blocks involved in the rigid amorphous fraction (RAF). An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as semicrystalline structure in each copolymer. Molecular motion within the copolymer systems is monitored by dielectric and nuclear magnetic resonance spectroscopies. The results reported herein reveal the existence of two local Arrhenius-type processes attributed to the noncooperative local motion of PEO segments involved in fully amorphous and rigid amorphous PEO microphases. In both systems, two structural relaxations governed by glass-transition phenomena are identified and assigned to cooperative segmental motion in the fully amorphous phase (the α process) and the RAF (the α c process). We measure the temperature dependence of the dynamics associated with all of the processes mentioned above and propose that these local processes are associated with corresponding cooperative segmental motion in both copolymer systems. In marked contrast to the thermal activation of the α process as discerned in both copolymers, the α c process appears to be a sensitive probe of the copolymer nanostructure. That is, the copolymer with shorter PEO blocks exhibits more highly restricted cooperative dynamics of PEO segments in the RAF, which can be explained in terms of the greater constraint imposed by the glassy PS matrix on the PEO blocks comprising smaller cylindrical microdomains.

Combined effect of cortical cytoskeleton and transmembrane proteins on domain formation in biomembranes

PubMed Central

Sikder, Md. Kabir Uddin; Stone, Kyle A.; Kumar, P. B. Sunil; Laradji, Mohamed

2014-01-01

We investigate the combined effects of transmembrane proteins and the subjacent cytoskeleton on the dynamics of phase separation in multicomponent lipid bilayers using computer simulations of a particle-based implicit solvent model for lipid membranes with soft-core interactions. We find that microphase separation can be achieved by the protein confinement by the cytoskeleton. Our results have relevance to the finite size of lipid rafts in the plasma membrane of mammalian cells. PMID:25106608

Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid–Polymer Hybrid Membranes

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

Kang, Minjee; Lee, Byeongdu; Leal, Cecilia

Here, we present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidencemore » that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid–polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid–polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications« less

Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid–Polymer Hybrid Membranes

DOE PAGES

Kang, Minjee; Lee, Byeongdu; Leal, Cecilia

2017-10-20

Here, we present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidencemore » that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid–polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid–polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications« less

Equilibrium Phase Behavior of a Continuous-Space Microphase Former.

PubMed

Zhuang, Yuan; Zhang, Kai; Charbonneau, Patrick

2016-03-04

Periodic microphases universally emerge in systems for which short-range interparticle attraction is frustrated by long-range repulsion. The morphological richness of these phases makes them desirable material targets, but our relatively coarse understanding of even simple models hinders controlling their assembly. We report here the solution of the equilibrium phase behavior of a microscopic microphase former through specialized Monte Carlo simulations. The results for cluster crystal, cylindrical, double gyroid, and lamellar ordering qualitatively agree with a Landau-type free energy description and reveal the nontrivial interplay between cluster, gel, and microphase formation.

Minimum free-energy paths for the self-organization of polymer brushes.

PubMed

Gleria, Ignacio; Mocskos, Esteban; Tagliazucchi, Mario

2017-03-22

A methodology to calculate minimum free-energy paths based on the combination of a molecular theory and the improved string method is introduced and applied to study the self-organization of polymer brushes under poor solvent conditions. Polymer brushes in a poor solvent cannot undergo macroscopic phase separation due to the physical constraint imposed by the grafting points; therefore, they microphase separate forming aggregates. Under some conditions, the theory predicts that the homogeneous brush and the aggregates can exist as two different minima of the free energy. The theoretical methodology introduced in this work allows us to predict the minimum free-energy path connecting these two minima as well as the morphology of the system along the path. It is shown that the transition between the homogeneous brush and the aggregates may involve a free-energy barrier or be barrierless depending on the relative stability of the two morphologies and the chain length and grafting density of the polymer. In the case where a free-energy barrier exists, one of the morphologies is a metastable structure and, therefore, the properties of the brush as the quality of the solvent is cycled are expected to display hysteresis. The theory is also applied to study the adhesion/deadhesion transition between two opposing surfaces modified by identical polymer brushes and it is shown that this process may also require surpassing a free-energy barrier.

Hydrophobic nanoparticles promote lamellar to inverted hexagonal transition in phospholipid mesophases.

PubMed

Bulpett, Jennifer M; Snow, Tim; Quignon, Benoit; Beddoes, Charlotte M; Tang, T-Y D; Mann, Stephen; Shebanova, Olga; Pizzey, Claire L; Terrill, Nicholas J; Davis, Sean A; Briscoe, Wuge H

2015-12-07

This study focuses on how the mesophase transition behaviour of the phospholipid dioleoyl phosphatidylethanolamine (DOPE) is altered by the presence of 10 nm hydrophobic and 14 nm hydrophilic silica nanoparticles (NPs) at different concentrations. The lamellar to inverted hexagonal phase transition (Lα-HII) of phospholipids is energetically analogous to the membrane fusion process, therefore understanding the Lα-HII transition with nanoparticulate additives is relevant to how membrane fusion may be affected by these additives, in this case the silica NPs. The overriding observation is that the HII/Lα boundaries in the DOPE p-T phase diagram were shifted by the presence of NPs: the hydrophobic NPs enlarged the HII phase region and thus encouraged the inverted hexagonal (HII) phase to occur at lower temperatures, whilst hydrophilic NPs appeared to stabilise the Lα phase region. This effect was also NP-concentration dependent, with a more pronounced effect for higher concentration of the hydrophobic NPs, but the trend was less clear cut for the hydrophilic NPs. There was no evidence that the NPs were intercalated into the mesophases, and as such it was likely that they might have undergone microphase separation and resided at the mesophase domain boundaries. Whilst the loci and exact roles of the NPs invite further investigation, we tentatively discuss these results in terms of both the surface chemistry of the NPs and the effect of their curvature on the elastic bending energy considerations during the mesophase transition.

Recent Advances in the Theory and Simulation of Model Colloidal Microphase Formers.

PubMed

Zhuang, Yuan; Charbonneau, Patrick

2016-08-18

This mini-review synthesizes our understanding of the equilibrium behavior of particle-based models with short-range attractive and long-range repulsive (SALR) interactions. These models, which can form stable periodic microphases, aim to reproduce the essence of colloidal suspensions with competing interparticle interactions. Ordered structures, however, have yet to be obtained in experiments. In order to better understand the hurdles to periodic microphase assembly, marked theoretical and simulation advances have been made over the past few years. Here, we present recent progress in the study of microphases in models with SALR interactions using liquid-state theory and density-functional theory as well as numerical simulations. Combining these various approaches provides a description of periodic microphases, and gives insights into the rich phenomenology of the surrounding disordered regime. Ongoing research directions in the thermodynamics of models with SALR interactions are also presented.

Guiding nanocrystal organization within mesoscale lipid thin-film templates

NASA Astrophysics Data System (ADS)

Steer, Dylan; Zhai, You; Oh, Nuri; Shim, Moonsub; Leal, Cecilia

Recently a great deal of interest has been established in the cooperative intermolecular interactions in hard and soft meso-structured composite materials. Much of this research has focused on the effects of nanoparticle incorporation into block copolymers that otherwise self-assemble into periodic mesostructures through microphase separation. Through careful selection of the polymer components the nanoparticles can be directed to also microphase separate and therefore exhibit symmetry induced by the block copolymers. Such systems are promising for enabling the organization of nanoparticle superstructures. Although this is useful in many applications such as in bottom-up assembly of opti-electronic materials, most of these applications would benefit from interplay between structure and dynamics. Much like block-copolymers, lipids can self-assembly into a variety of structures with 1D lamellar, 2D Hexagonal, and 3D cubic symmetry. However, unlike block-copolymers phase stabilization and conversion from one geometry to another happens under a minute. We will show our recent efforts into using lipid thin films to guide the assembly of nanoparticle superstructures resembling those displayed by lipid polymorphs and how they distort lipid equilibrium phase behavior. Funding from the Office of Naval Research.

Tough and Sustainable Graft Block Copolymer Thermoplastics

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

Zhang, Jiuyang; Li, Tuoqi; Mannion, Alexander M.

Fully sustainable poly[HPMC-g-(PMVL-b-PLLA)] graft block copolymer thermoplastics were prepared from hydroxypropyl methylcellulose (HPMC), β-methyl-δ-valerolactone (MVL), and l-lactide (LLA) using a facile two-step sequential addition approach. In these materials, rubbery PMVL functions as a bridge between the semirigid HPMC backbone and the hard PLLA end blocks. This specific arrangement facilitates PLLA crystallization, which induces microphase separation and physical cross-linking. By changing the backbone molar mass or side chain composition, these thermoplastic materials can be easily tailored to access either plastic or elastomeric behavior. Moreover, the graft block architecture can be utilized to overcome the processing limitations inherent to linear block polymers.more » Good control over molar mass and composition enables the deliberate design of HPMC-g-(PMVL-b-PLLA) samples that are incapable of microphase separation in the melt state. These materials are characterized by relatively low zero shear viscosities in the melt state, an indication of easy processability. The simple and scalable synthetic procedure, use of inexpensive and renewable precursors, and exceptional rheological and mechanical properties make HPMC-g-(PMVL-b-PLLA) polymers attractive for a broad range of applications.« less

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

PubMed

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

2017-06-07

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

Dynamics and order-disorder transitions in bidisperse diblock copolymer blends

NASA Astrophysics Data System (ADS)

Wang, Yueqiang; Li, Xuan; Tang, Ping; Yang, Yuliang

2011-03-01

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.

Thermoset nanocomposites from two-component waterborne polyurethanes and cellulose whiskers.

PubMed

Wu, Guo-min; Chen, Jian; Huo, Shu-ping; Liu, Gui-feng; Kong, Zhen-wu

2014-05-25

We prepared thermoset nancomposites from biomass-based two-component waterborne polyurethane (2K-WPU) and cellulose namowhiskers (CNWs). Due to the formation of hydrogen bonds, the viscosity of 2K-WPU dispersion was found to be increased with the addition of CNWs. SEM images showed "sea-island structure" corresponding to the microphase separation between CNWs nano-filler and the 2K-WPU matrix. The α-relaxation temperature (Tα) and glass transition temperature (Tg) increased with the increase of CNWs content, which was due to the formation of a rigid CNWs nano-phase acting as crosslinking points in the 2K-WPU matrix. Mechanical properties from tensile test showed Young's modulus and tensile strength of 2K-WPU/CNWs nanocomposites were reinforced by the addition of CNWs. Thermo-stability of 2K-WPU/CNWs nanocomposites decreased slightly with the increase of CNWs content, which could be attributed to the increased thermal conductivity of the material after adding CNWs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Magneto-Adaptive Surfactants Showing Anti-Curie Behavior and Tunable Surface Tension as Porogens for Mesoporous Particles with 12-Fold Symmetry.

PubMed

Hermann, Stefanie; Wessig, Martin; Kollofrath, Dennis; Gerigk, Melanie; Hagedorn, Kay; Odendal, James A; Hagner, Matthias; Drechsler, Markus; Erler, Philipp; Fonin, Mikhail; Maret, Georg; Polarz, Sebastian

2017-05-08

Gaining external control over self-organization is of vital importance for future smart materials. Surfactants are extremely valuable for the synthesis of diverse nanomaterials. Their self-assembly is dictated by microphase separation, the hydrophobic effect, and head-group repulsion. It is desirable to supplement surfactants with an added mode of long-range and directional interaction. Magnetic forces are ideal, as they are not shielded in water. We report on surfactants with heads containing tightly bound transition-metal centers. The magnetic moment of the head was varied systematically while keeping shape and charge constant. Changes in the magnetic moment of the head led to notable differences in surface tension, aggregate size, and contact angle, which could also be altered by an external magnetic field. The most astonishing result was that the use of magnetic surfactants as structure-directing agents enabled the formation of porous solids with 12-fold rotational symmetry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A New Supramolecular Route for Using Rod-Coil Block Copolymers in Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Mezzenga, Raffaele; Sary, Nicolas; Richard, Fanny; Brochon, Cyril; Leclerc, Nicolas; Leveque, Patrick; Audinot, Jean Nicolas; Heiser, Thomas; Hadziioannou, Georges; Berson, Solenn

2010-03-01

We propose a new supramolecular strategy to blend together rod-coil poly(3-hexylthiophene)-poly(4-vinylpyridine) (P3HTP4VP) block copolymers and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The P4VP and PCBM are mixed together by weak supramolecular interactions, and the resulting materials exhibit microphase separated morphologies of electron-donor and electron-acceptor rich domains. The microphase segregated P3HT-rod domains act as electron-donating species and the homogeneous P4VP block:PCBM blend acts as the electron-acceptor domain. We describe the photovoltaic performance of standard and inverted devices whose active layer is composed thereof and show the effect of finely engineering the interfacial properties of the active layer to obtain competitive photovoltaic performance with superior thermal stability. (1) N. Sary, F. Richard, C. Brochon, N. Leclerc, P. Leveque, JN Audinot, S. Berson, T. Heiser, G. Hadziioannou, R. Mezzenga, Adv. Mater. in Press (2010)

Aggregate morphologies of amphiphilic ABC triblock copolymer in dilute solution using self-consistent field theory.

PubMed

Wang, Rong; Tang, Ping; Qiu, Feng; Yang, Yuliang

2005-09-15

The complex microstructures of amphiphilic ABC linear triblock copolymers in which one of the end blocks is relatively short and hydrophilic, and the other two blocks B and C are hydrophobic in a dilute solution, have been investigated by the real-space implementation of self-consistent field theory (SCFT) in two dimensions (2D). In contrast to diblock copolymers in solution, the aggregation of triblock copolymers are more complicated due to the presence of the second hydrophobic blocks and, hence, big ranges of parameter space controlling the morphology. By tailoring the hydrophobic degree and its difference between the blocks B and C, the various shapes of vesicles, circlelike and linelike micelles possibly corresponding to spherelike, and rodlike micelles in 3D, and especially, peanutlike micelles not found in diblock copolymers are observed. The transition from vesicles to circlelike micelles occurs with increasing the hydrophobicity of the blocks B and C, while the transition from circlelike micelles to linelike micelles or from the mixture of micelles and vesicles to the long linelike micelles takes place when the repulsive interaction of the end hydrophobic block C is stronger than that of the middle hydrophobic block B. Furthermore, it is favorable for dispersion of the block copolymer in the solvent into aggregates when the repulsion of the solvent to the end hydrophobic block is larger than that of the solvent to the middle hydrophobic block. Especially when the bulk block copolymers are in a weak segregation regime, the competition between the microphase separation and macrophase separation exists and the large compound micelle-like aggregates are found due to the macrophase separation with increasing the hydrophobic degree of blocks B and C, which is absent in diblock copolymer solution. The simulation results successfully reproduce the existing experimental ones.

Directed Self-Assembly of Star-Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism.

PubMed

Krishnan, Mohan Raj; Lu, Kai-Yuan; Chiu, Wen-Yu; Chen, I-Chen; Lin, Jheng-Wei; Lo, Ting-Ya; Georgopanos, Prokopios; Avgeropoulos, Apostolos; Lee, Ming-Chang; Ho, Rong-Ming

2018-04-01

Exploring the ordering mechanism and dynamics of self-assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self-assembling mechanism and kinetics of silicon-containing 3-arm star-block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self-assembly using topographically patterned substrates. The ordering process of the star-block copolymer within fabricated topographic patterns with PS-functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well-ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self-assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top-down and bottom-up approaches. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

NASA Astrophysics Data System (ADS)

Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

2014-08-01

High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

Microphase separation in solid lipid dosage forms as the cause of drug release instability.

PubMed

Lopes, Diogo Gomes; Koutsamanis, Ioannis; Becker, Karin; Scheibelhofer, Otto; Laggner, Peter; Haack, Detlev; Stehr, Michael; Zimmer, Andreas; Salar-Behzadi, Sharareh

2017-01-30

Although lipid excipients are of increasing interest for development of taste-masked and modified release formulations, the drug release instability and the lack of mechanistic understanding in that regard still prevent their larger-scale application. In this work, we investigated the physical stability of a binary (tripalmitin/polysorbate 65) lipid coating formulation with a known stable polymorphism. The coating composition was characterized using DSC to construct the phase diagram of binary system and polarized light microscopy to display the microstructure organization. The water uptake and the erosion of slabs cast from the coating formulations were investigated post-production and after storage. Subsequently, N-acetylcysteine particles were coated with the selected formulations and the drug release stability was investigated. Additionally, microstructure characterization was performed via SEM and X-ray diffraction. The drug release instability was explained by polysorbate 65 and tripalmitin phase growth during storage, especially at 40°C, suggesting that polysorbate 65 can leak out of tripalmitin spherulitic structures, creating lipophilic and impermeable tripalmitin regions. The growth of polysorbate 65 phase leads to larger hydrophilic channels with reduced tortuosity. This work indicates that for obtaining stable drug release profiles from advanced lipid formulations, microphase separation should be prevented during storage. Copyright © 2016 Elsevier B.V. All rights reserved.

Clustering and assembly dynamics of a one-dimensional microphase former.

PubMed

Hu, Yi; Charbonneau, Patrick

2018-05-23

Both ordered and disordered microphases ubiquitously form in suspensions of particles that interact through competing short-range attraction and long-range repulsion (SALR). While ordered microphases are more appealing materials targets, understanding the rich structural and dynamical properties of their disordered counterparts is essential to controlling their mesoscale assembly. Here, we study the disordered regime of a one-dimensional (1D) SALR model, whose simplicity enables detailed analysis by transfer matrices and Monte Carlo simulations. We first characterize the signature of the clustering process on macroscopic observables, and then assess the equilibration dynamics of various simulation algorithms. We notably find that cluster moves markedly accelerate the mixing time, but that event chains are of limited help in the clustering regime. These insights will inspire further study of three-dimensional microphase formers.

Understanding ion association states and molecular dynamics using infrared spectroscopy

NASA Astrophysics Data System (ADS)

Masser, Hanqing

A molecular level understanding of the ion transport mechanism within polymer electrolytes is crucial to the further development for advanced energy storage applications. This can be achieved by the identification and quantitative measurement of different ion species in the system and further relating them to the ion conductivity. In the first part of this thesis, research is presented towards understanding the ion association states (free ions, ion pairs and ion aggregates) in ionomer systems, and the correlation of ion association states, ion conduction, polymer dynamics, and morphology. Ion conductivity in ionomers can be improved by lowering glass transition temperature, increasing polymer ion solvation ability, and adjusting ionomer structural variables such as ion content, cation type and side chain structure. These effects are studied in three ionomer systems respectively, using a combination of characterization methods. Fourier Transform Infrared Spectroscopy (FTIR) identifies and quantifies the ion association states. Dielectric Spectroscopy (DRS) characterizes ion conductivity and polymer and ion dynamics. X-ray scattering reveals changes in morphology. The influence of a cation solvating plasticizer on a polyester ionomer is systematically investigated with respect to ion association states, ion and polymer dynamics and morphology. A decrease in the number ratio of ion aggregates with increased plasticizer content and a slight increase at elevated temperature are observed in FTIR. Similar results are also detected by X-ray scattering. As determined from dielectric spectroscopy, ion conductivity increases with plasticizer content, in accordance with the decrease in glass transition temperature. Research on copolymer of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) based ionomers further develops an understanding of the trade-off between ion solvation and segmental dynamics. Upon the incorporation of PTMO, the majority of the PTMO microphase separates from the PEO-rich microphase, and ionic groups are preferentially solvated by PEO chains and reside in the PEO-rich microphase. As the ratio of PTMO increases, the fraction of aggregates increases, resulting in more highly coordinated aggregation states. Results on ion association states are in good agreement with previous results on ion conductivity, polymer dynamics and morphology. The effects of ion content, cation type and ionic side chain structure on ion association states are systemically studied in a series of ionomers with short ethylene oxide and ionic sulfonated styrene side chains, and then correlated to the ion and polymer dynamic characterization. It is found that ionomers with modest ion content, large cation and styrene ionic side chain have the most "free ions" and ion pairs, and highest ion conductivity. Ion conduction in ionomers is optimized by systematically changing their chemical structures. In addition to knowledge of ion association states, a IR band shape also contains information on molecular dynamics. In companion investigation, the vibrational relaxation and dynamic transitions of conformationally insensitive normal modes in two different polymer systems (atactic polystyrene and deuterated poly(methyl methacrylate)) are studied. The information on vibrational relaxations is resolved by conducting precisely controlled FTIR experiments, applying specialized curve resolving data analysis, and calculating time correlation functions through numerical Fourier transformation. The vibrational relaxations of these modes can be described by a two process model: a fast process on the time scale of 0.01 ps, which is inhomogeneously broadened by a slow process on the time scale of picoseconds.

Interpreting Neutron Reflectivity Profiles of Diblock Copolymer Nanocomposite Thin Films Using Hybrid Particle-Field Simulations

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

Mahalik, Jyoti P.; Dugger, Jason W.; Sides, Scott W.

Mixtures of block copolymers and nanoparticles (block copolymer nanocomposites) are known to microphase separate into a plethora of microstructures, depending on the composition, length scale and nature of interactions among its different constituents. Theoretical and experimental works on this class of nanocomposites have already high-lighted intricate relations among chemical details of the polymers, nanoparticles, and various microstructures. Confining these nanocomposites in thin films yields an even larger array of structures, which are not normally observed in the bulk. In contrast to the bulk, exploring various microstructures in thin films by the experimental route remains a challenging task. Here in thismore » work, we construct a model for the thin films of lamellar forming diblock copolymers containing spherical nanoparticles based on a hybrid particle-field approach. The model is benchmarked by comparison with the depth profiles obtained from the neutron reflectivity experiments for symmetric poly(deuterated styrene-b-n butyl methacrylate) copolymers blended with spherical magnetite nanoparticles covered with hydrogenated poly(styrene) corona. We show that the model based on a hybrid particle-field approach provides details of the underlying microphase separation in the presence of the nanoparticles through a direct comparison to the neutron reflectivity data. This work benchmarks the application of the hybrid particle-field model to extract the interaction parameters for exploring different microstructures in thin films containing block copolymers and nanocomposites.« less

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

PubMed

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.

Interpreting Neutron Reflectivity Profiles of Diblock Copolymer Nanocomposite Thin Films Using Hybrid Particle-Field Simulations

DOE PAGES

Mahalik, Jyoti P.; Dugger, Jason W.; Sides, Scott W.; ...

2018-04-10

Mixtures of block copolymers and nanoparticles (block copolymer nanocomposites) are known to microphase separate into a plethora of microstructures, depending on the composition, length scale and nature of interactions among its different constituents. Theoretical and experimental works on this class of nanocomposites have already high-lighted intricate relations among chemical details of the polymers, nanoparticles, and various microstructures. Confining these nanocomposites in thin films yields an even larger array of structures, which are not normally observed in the bulk. In contrast to the bulk, exploring various microstructures in thin films by the experimental route remains a challenging task. Here in thismore » work, we construct a model for the thin films of lamellar forming diblock copolymers containing spherical nanoparticles based on a hybrid particle-field approach. The model is benchmarked by comparison with the depth profiles obtained from the neutron reflectivity experiments for symmetric poly(deuterated styrene-b-n butyl methacrylate) copolymers blended with spherical magnetite nanoparticles covered with hydrogenated poly(styrene) corona. We show that the model based on a hybrid particle-field approach provides details of the underlying microphase separation in the presence of the nanoparticles through a direct comparison to the neutron reflectivity data. This work benchmarks the application of the hybrid particle-field model to extract the interaction parameters for exploring different microstructures in thin films containing block copolymers and nanocomposites.« less

Thermoset nanocomposites from waterborne bio-based epoxy resin and cellulose nanowhiskers.

PubMed

Wu, Guo-min; Liu, Di; Liu, Gui-feng; Chen, Jian; Huo, Shu-ping; Kong, Zhen-wu

2015-01-01

Thermoset nanocomposites were prepared from a waterborne terpene-maleic ester type epoxy resin (WTME) and cellulose nanowhiskers (CNWs). The curing behaviors of WTME/CNWs nanocomposites were measured with rotational rheometer. The results show that the storage modulus (G') of WTME/CNWs nanocomposites increased with the increase of CNWs content. Observations by scanning electron microscopy (SEM) demonstrate that the incorporation of CNWs in WTME matrix caused microphase separation and destroyed the compactness of the matrix. This effect leads to the glass transition temperatures (Tg) of WTME/CNWs nanocomposites slightly decrease with the increase of CNWs content, which were confirmed by both DSC and DMA tests. The mechanical properties of WTME/CNWs nanocomposites were investigated by tensile testing. The Yong's modulus (E) and tensile strength (σb) of the nanocomposites were significantly reinforced by the addition of CNWs. These results indicate that CNWs exhibit excellent reinforcement effect on WTME matrix, due to the formation and increase of interfacial interaction by hydrogen bonds between CNWs nano-filler and the WTME matrix. Copyright © 2015 Elsevier Ltd. All rights reserved.

Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior

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

Ashraf, Arman R.; Ryan, Justin J.; Satkowski, Michael M.

Block copolymers have been extensively studied due to their ability to spontaneously self-organize into a wide variety of morphologies that are valuable in energy-, medical- and conservation-related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, we demonstrate that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks is a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms ofmore » the order-disorder transition (ODT), has been investigated. Our results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase-separate. We also report that the predicted ODT can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence-controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random-copolymer midblock.« less

Morphological Characterization of Silicone Hydrogels

NASA Astrophysics Data System (ADS)

Gido, Samuel

2007-03-01

Silicone hydrogel materials are used in the latest generation of extended wear soft contact lenses. To ensure comfort and eye health, these materials must simultaneously exhibit high oxygen permeability and high water permeability / hydrophilicity. The materials achieve these opposing requirements based on bicontinuous composite of nanoscale domains of oxygen permeable (silicones) and hydrophilic (water soluble polymer) materials. The microphase separated morphology of silicone hydrogel contact lens materials was imaged using field emission gun scanning transmission electron microscopy (FEGSTEM), and atomic force microscopy (AFM). Additional morphological information was provided by small angle X-ray scattering (SAXS). These results all indicate a nanophase separated structure of silicone rich (oxygen permeable) and carbon rich (water soluble polymer) domains separated on a length scale of about 10 nm.

Polyurethane foams based on crude glycerol-derived biopolyols: One-pot preparation of biopolyols with branched fatty acid ester chains and its effects on foam formation and properties

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

Li, Cong; Luo, Xiaolan; Li, Tao

2014-01-01

Environmentally friendly biopolyols have been produced with crude glycerol as the sole feedstock using a one-pot thermochemical conversion process without the addition of extra catalysts and reagents. Structural features of these biopolyols were characterized by rheology analysis. Rigid polyurethane (PU) foams were obtained from these crude glycerol-based biopolyols and the foaming mechanism was explored. Investigations revealed that partial carbonyl groups hydrogen-bonded with NeH were replaced by aromatic rings after the introduction of branched fatty acid ester chains in the “urea rich” phase, and that distinct microphases had formed in the foams. Studies showed that branched fatty acid ester chains inmore » the biopolyols played an important role in reducing the degree of microphase separation and stabilizing bubbles during foaming processes. PU foams with thermal conductivity comparable to commercial products made from petroleum-based polyols were obtained. These studies show the potential for development of PU foams based on crude glycerol, a renewable resource.« less

Development of Self-Assembled Nanoscale Templates via Microphase Separation Induced by Polymer Brushes

NASA Astrophysics Data System (ADS)

Chu, Elza

Phase separation in soft matter has been the crucial element in generating hybrid materials, such as polymer blends and mixed polymer brushes. This dissertation discusses two methods of developing self-assembled nanoscale templates via microphase separation induced by polymer brush synthesis. This work introduces a novel soft substrate approach with renewable grafting sites where polyacrylamide is "grafted through" chitosan soft substrates. The mechanism of grafting leads to ordered arrays of filament-like nanostructures spanning the chitosan-air interface. Additionally, the chemical composition of the filaments allows for post-chemical modification to change the physical properties of the filaments, and subsequently tailor surfaces for specific application. Unlike traditional materials, multi-functional or "smart" materials, such as binary polymer brushes (BPB) are capable of spontaneously changing the spatial distribution of functional groups and morphology at the surface upon external stimuli. Although promising in principle, the limited range of available complementary polymers with common non-selective solvents confines the diversity of usable materials and restricts any further advancement in the field. This dissertation also covers the fabrication and characterization of responsive nanoscale polystyrene templates or "mosaic" brushes that are capable of changing interfacial composition upon exposure to varying solvent qualities. Using a "mosaic" brush template is a unique approach that allows the fabrication of strongly immiscible polymer BPB without the need for a common solvent. The synthesis of such BPB is exemplified by two strongly immiscible polymers, i.e. polystyrene (polar) and polyacrylamide (non-polar), where polyacrylamide brush is "graft through" a Si-substrate modified with the polystyrene collapsed "mosaic" brush. The surface exhibits solvent-triggered responses, as well as application potential for anti-biofouling.

A New Strategy to Prepare Polymer-based Shape Memory Elastomers.

PubMed

Song, Shijie; Feng, Jiachun; Wu, Peiyi

2011-10-04

A new strategy that utilizes the microphase separation of block copolymer and phase transition of small molecules for preparing polymer-based shape memory elastomer has been proposed. According to this strategy, a novel kind of shape memory elastomer comprising styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and paraffin has been prepared. Because paraffins are midblock-selective molecules for SEBS, they will preferentially enter and swell EB blocks supporting paraffins as an excellent switch phase for shape memory effect. Microstructures of SEBS/paraffin composites have been characterized by transmission electron microscopy, polarized light microscopy, and differential scanning calorimetry. The composites demonstrate various phase morphologies with regard to different paraffin loading. It has been found that under low paraffin loading, all the paraffins precisely embed in and swell EB-rich domains. While under higher loading, part of the paraffins become free and a larger-scaled phase separation has been observed. However, within wide paraffin loadings, all composites show good shape fixing, shape recovery performances, and improved tensile properties. Compared to the reported methods for shape memory elastomers preparation, this method not only simplifies the fabrication procedure from raw materials to processing but also offers a controllable approach for the optimization of shape memory properties as well as balancing the rigidity and softness of the material. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium water and solute uptake in silicone hydrogels.

PubMed

Liu, D E; Dursch, T J; Oh, Y; Bregante, D T; Chan, S Y; Radke, C J

2015-05-01

Equilibrium water content of and solute partitioning in silicone hydrogels (SiHys) are investigated using gravimetric analysis, fluorescence confocal laser-scanning microscopy (FCLSM), and back extraction with UV/Vis-absorption spectrophotometry. Synthesized silicone hydrogels consist of silicone monomer, hydrophilic monomer, cross-linking agent, and triblock-copolymer macromer used as an amphiphilic compatibilizer to prevent macrophase separation. In all cases, immiscibility of the silicone and hydrophilic polymers results in microphase-separated morphologies. To investigate solute uptake in each of the SiHy microphases, equilibrium partition coefficients are obtained for two hydrophilic solutes (i.e., theophylline and caffeine dissolved in aqueous phosphate-buffered saline) and two oleophilic solutes (i.e., Nile Red and Bodipy Green dissolved in silicone oil), respectively. Measured water contents and aqueous-solute partition coefficients increase linearly with increasing solvent-free hydrophilic-polymer volume fraction. Conversely, oleophilic-solute partition coefficients decrease linearly with rising solvent-free hydrophilic-polymer volume fraction (i.e., decreasing hydrophobic silicone-polymer fraction). We quantitatively predict equilibrium SiHy water and solute uptake assuming that water and aqueous solutes reside only in hydrophilic microdomains, whereas oleophilic solutes partition predominately into silicone microdomains. Predicted water contents and solute partition coefficients are in excellent agreement with experiment. Our new procedure permits a priori estimation of SiHy water contents and solute partition coefficients based solely on properties of silicone and hydrophilic homopolymer hydrogels, eliminating the need for further mixed-polymer-hydrogel experiments. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The Influence of Charged Species on the Phase Behavior, Self-Assembly, and Electrochemical Performance of Block Copolymer Electrolytes

NASA Astrophysics Data System (ADS)

Thelen, Jacob Lloyd

One of the major barriers to expanding the capacity of large-scale electrochemical energy storage within batteries is the threat of a catastrophic failure. Catastrophic battery pack failure can be initiated by a defect within a single battery cell. If the failure of a defective battery cell is not contained, the damage can spread and subsequently compromise the integrity of the entire battery back, as well as the safety of those in its surroundings. Replacing the volatile, flammable liquid electrolyte components found in most current lithium ion batteries with a solid polymer electrolyte (SPE) would significantly improve the cell-level safety of batteries; however, poor ionic conductivity and restricted operating temperatures compared to liquid electrolytes have plagued the practical application of SPEs. Rather than competing with the performance of liquid electrolytes directly, our approach to developing SPEs relies on increasing electrolyte functionality through the use of block copolymer architectures. Block copolymers, wherein two or more chemically dissimilar polymer chains are covalently bound, have a propensity to microphase separate into nanoscale domains that have physical properties similar to those of each of the different polymer chains. For instance, the block copolymer, polystyrene-b-poly(ethylene oxide) (SEO), has often been employed as a solid polymer electrolyte because the nanoscale domains of polystyrene (PS) can provide mechanical reinforcement, while the poly(ethylene oxide) microphases can solvate and conduct lithium ions. Block copolymer electrolytes (BCEs) formed from SEO/salt mixtures result in a material with the bulk mechanical properties of a solid, but with the ion conducting properties of a viscoelastic fluid. The efficacy SEO-based BCEs has been demonstrated; the enhanced mechanical functionality provided by the PS domains resist the propagation of dendritic lithium structures during battery operation, thus enabling the use of a lithium metal anode. The increase in the specific energy of a battery upon replacing a graphite anode with lithium metal can offset the losses in performance due to the poor ion conduction of SPEs. However, BCEs that enable the use of a lithium anode and have improved performance would represent a major breakthrough for the development of high capacity batteries. The electrochemical performance of BCEs has a complex relationship with the nature of the microphase separated domains, which is not well-understood. The objective of this dissertation is to provide fundamental insight into the nature of microphase separation and self-assembly of block copolymer electrolytes. Specifically, I will focus on how the ion-polymer interactions within a diverse set of BCEs dictate nanostructure. Combining such insight with knowledge of how nanostructure influences ion motion will enable the rational design of new BCEs with enhanced performance and functionality. In order to facilitate the study of BCE nanostructure, synchrotron-based X-ray scattering techniques were used to study samples over a wide range of length-scales under conditions relevant to the battery environment. The development of the experimental aspects of the X-ray scattering techniques, as well as an improved treatment of scattering data, played a pivotal role in the success of this work. The dissemination of those developments will be the focus of the first section. The thermodynamic impact of adding salt to a neutral diblock copolymer was studied in a model BCE composed of a low molecular weight SEO diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), a common salt used in lithium batteries. In neutral block copolymers (BCPs), self-assembly is a thermodynamically driven process governed by a balance between unfavorable monomer contacts and the entropy of mixing. When the enthalpic and entropic contributions to free energy are similar in magnitude, a block copolymer can undergo a thermally reversible phase transition from an ordered to a disordered nanostructure. We used temperature-dependent small angle X-ray scattering (SAXS) to observe this transition in the model SEO/LiTFSI system. Unlike neutral BCPs, which to a first approximation are single component systems, the SEO/LiTFSI system demonstrated the thermodynamically stable coexistence phases of ordered lamellae and disordered polymer over a finite temperature window. Analysis of the lamellar domains revealed an increase in salt concentration during the ODT, indicating local salt partitioning due to the presence of nanostructure. The performance of BCEs can also be improved by chemically functionalizing one of the polymer blocks by covalently attaching the salt anion. Since the cation is the only mobile species, these materials are coined single-ion conducting block copolymers. Single ion conduction can improve the efficiency of battery operation. In order for cation motion to occur in single-ion conducting block copolymers, it must dissociate from the backbone of the anion-containing polymer block. This direct coupling of ion dissociation (and hence conduction) and nanostructure has interesting implications for BCE performance. (Abstract shortened by ProQuest.).

Phase Separation During the Curing of a Cyanate Ester Oligomer

NASA Astrophysics Data System (ADS)

Gurov, D. A.; Novikov, G. F.

2018-07-01

It is found during the curing of a cyanate ester oligomer that there are such features as a step and a maximum in the frequency dependences (in a range of 10-2-105 Hz) of the real parts of the complex electric conductivity and loss tangent, respectively. In the frequency range where these features are observed, the diagrams of complex electric modulus are semicircles with centers near the abscissas. Subsequent analysis shows these features are due to the formation of the microphase of the intermediate product, carbamate.

ABC Triblock Copolymer Vesicles with Mesh-like Morphology

NASA Astrophysics Data System (ADS)

Zhao, Wei; Russell, Thomas; Grason, Gregory

2010-03-01

Polymer vesicles can be made from poly(isoprene-b-styrene-b-2-vinylpyridene) (PI-b-PS-b-P2VP) triblock copolymer under the confinement of anodic aluminum oxide (AAO) membrane. It was found that these vesicles have well-defined, nanoscopic size and a microphase-separated hydrophobic core, comprised of PS and PI blocks. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the core at a well-defined composition of three blocks. Confinement played an important role in generating these vesicles with such an unusual morphology.

Main-chain supramolecular block copolymers.

PubMed

Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

2011-01-01

Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

Tough stimuli-responsive supramolecular hydrogels with hydrogen-bonding network junctions.

PubMed

Guo, Mingyu; Pitet, Louis M; Wyss, Hans M; Vos, Matthijn; Dankers, Patricia Y W; Meijer, E W

2014-05-14

Hydrogels were prepared with physical cross-links comprising 2-ureido-4[1H]-pyrimidinone (UPy) hydrogen-bonding units within the backbone of segmented amphiphilic macromolecules having hydrophilic poly(ethylene glycol) (PEG). The bulk materials adopt nanoscopic physical cross-links composed of UPy-UPy dimers embedded in segregated hydrophobic domains dispersed within the PEG matrix as comfirmed by cryo-electron microscopy. The amphiphilic network was swollen with high weight fractions of water (w(H2O) ≈ 0.8) owing to the high PEG weight fraction within the pristine polymers (w(PEG) ≈ 0.9). Two different PEG chain lengths were investigated and illustrate the corresponding consequences of cross-link density on mechanical properties. The resulting hydrogels exhibited high strength and resilience upon deformation, consistent with a microphase separated network, in which the UPy-UPy interactions were adequately shielded within hydrophobic nanoscale pockets that maintain the network despite extensive water content. The cumulative result is a series of tough hydrogels with tunable mechanical properties and tractable synthetic preparation and processing. Furthermore, the melting transition of PEG in the dry polymer was shown to be an effective stimulus for shape memory behavior.

The Effect of Small Molecule Additives on the Self-Assembly and Functionality of Protein-Polymer Diblock Copolymers

NASA Astrophysics Data System (ADS)

Thomas, Carla; Xu, Liza; Olsen, Bradley

2013-03-01

Self-assembly of globular protein-polymer block copolymers into well-defined nanostructures provides a route towards the manufacture of protein-based materials which maintains protein fold and function. The model material mCherry-b-poly(N-isopropyl acrylamide) forms self-assembled nanostructures from aqueous solutions via solvent evaporation. To improve retention of protein functionality when dehydrated, small molecules such as trehalose and glycerol are added in solution prior to solvent removal. With as little as 10 wt% additive, improvements in retained functionality of 20-60% are observed in the solid-state as compared to samples in which no additive is present. Higher additive levels (up to 50%) continue to show improvement until approximately 100% of the protein function is retained. These large gains are hypothesized to originate from the ability of the additives to replace hydrogen bonds normally fulfilled by water. The addition of trehalose in the bulk material also improves the thermal stability of the protein by 15-20 °C, while glycerol decreases the thermal stability. Materials containing up to 50% additives remain microphase separated, and, upon incorporation of additives, nanostructure domain spacing tends to increase, accompanied by order-order transitions.

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

Park, Jongmin; Saba, Stacey A.; Hillmyer, Marc A.

We report on the phase separation behaviors of polymerization mixtures containing a polylactide macro-chain transfer agent (PLA-CTA), styrene, divinylbenzene, hydroxyl-terminated PLA (PLA-OH), and a molecular chain transfer agent which enable the ability to tune the pore size of a cross-linked polymer monolith in a facile manner. Cross-linked monoliths were produced from the mixtures via reversible addition-fragmentation chain transfer (RAFT) polymerization and converted into cross-linked porous polymers by selective removal of PLA while retaining the parent morphology. We demonstrate that pore sizes are tunable over a wide range of length scales from the meso- to macroporous regimes by adjusting the ratiomore » of PLA-CTA to PLA-OH in the reaction mixture which causes the phase separation mechanism to change from polymerization-induced microphase separation to polymerization-induced phase separation. The possibility of increasing porosity and inducing simultaneous micro- and macrophase separation was also realized by adjustments in the molar mass of PLA which enabled the synthesis of hierarchically meso- and macroporous polymers.« less

Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites

NASA Astrophysics Data System (ADS)

Bowman, Michelle Kathleen

Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a poly(styrene-b-methyl methacrylate) (SM) diblock copolymer with an order-disorder transition temperature (TODT) of 186°C, we find that the addition of clustered and discrete nanoparticles of varying size and surface selectivity can cause T ODT to generally decrease, but occasionally increase. Also experimenting with a poly(styrene-b-isoprene) (SI) diblock copolymer with an TODT of 116°C, we find that the addition of smaller nanoparticles at small volume fractions effect the TODT more profoundly. The latter unexpected results are likewise predicted by SCFT and provide a unique strategy by which to improve the nanostructure stability of block copolymers by physical means.

Chemical Interactions and Their Role in the Microphase Separation of Block Copolymer Thin Films

PubMed Central

Farrell, Richard A.; Fitzgerald, Thomas G.; Borah, Dipu; Holmes, Justin D.; Morris, Michael A.

2009-01-01

The thermodynamics of self-assembling systems are discussed in terms of the chemical interactions and the intermolecular forces between species. It is clear that there are both theoretical and practical limitations on the dimensions and the structural regularity of these systems. These considerations are made with reference to the microphase separation that occurs in block copolymer (BCP) systems. BCP systems self-assemble via a thermodynamic driven process where chemical dis-affinity between the blocks driving them part is balanced by a restorative force deriving from the chemical bond between the blocks. These systems are attracting much interest because of their possible role in nanoelectronic fabrication. This form of self-assembly can obtain highly regular nanopatterns in certain circumstances where the orientation and alignment of chemically distinct blocks can be guided through molecular interactions between the polymer and the surrounding interfaces. However, for this to be possible, great care must be taken to properly engineer the interactions between the surfaces and the polymer blocks. The optimum methods of structure directing are chemical pre-patterning (defining regions on the substrate of different chemistry) and graphoepitaxy (topographical alignment) but both centre on generating alignment through favourable chemical interactions. As in all self-assembling systems, the problems of defect formation must be considered and the origin of defects in these systems is explored. It is argued that in these nanostructures equilibrium defects are relatively few and largely originate from kinetic effects arising during film growth. Many defects also arise from the confinement of the systems when they are ‘directed’ by topography. The potential applications of these materials in electronics are discussed. PMID:19865513

Polyacylurethanes as Novel Degradable Cell Carrier Materials for Tissue Engineering

PubMed Central

Jovanovic, Danijela; Roukes, Frans V.; Löber, Andrea; Engels, Gerwin E.; van Oeveren, Willem; van Seijen, Xavier J. Gallego; van Luyn, Marja J.A.; Harmsen, Martin C.; Schouten, Arend Jan

2011-01-01

Polycaprolactone (PCL) polyester and segmented aliphatic polyester urethanes based on PCL soft segment have been thoroughly investigated as biodegradable scaffolds for tissue engineering. Although proven beneficial as long term implants, these materials degrade very slowly and are therefore not suitable in applications in which scaffold support is needed for a shorter time. A recently developed class of polyacylurethanes (PAUs) is expected to fulfill such requirements. Our aim was to assess in vitro the degradation of PAUs and evaluate their suitability as temporary scaffold materials to support soft tissue repair. With both a mass loss of 2.5–3.0% and a decrease in molar mass of approx. 35% over a period of 80 days, PAUs were shown to degrade via both bulk and surface erosion mechanisms. Fourier Transform Infra Red (FTIR) spectroscopy was successfully applied to study the extent of PAUs microphase separation during in vitro degradation. The microphase separated morphology of PAU1000 (molar mass of the oligocaprolactone soft segment = 1000 g/mol) provided this polymer with mechano-physical characteristics that would render it a suitable material for constructs and devices. PAU1000 exhibited excellent haemocompatibility in vitro. In addition, PAU1000 supported both adhesion and proliferation of vascular endothelial cells and this could be further enhanced by pre-coating of PAU1000 with fibronectin (Fn). The contact angle of PAU1000 decreased both with in vitro degradation and by incubation in biological fluids. In endothelial cell culture medium the contact angle reached 60°, which is optimal for cell adhesion. Taken together, these results support the application of PAU1000 in the field of soft tissue repair as a temporary degradable scaffold. PMID:28824103

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

Lu, Wei; Wang, Yangyang; Wang, Weiyu

All acrylic-based thermoplastic elastomers (TPEs) offer potential alternatives to the widely-used styrenic TPEs. However, the high entanglement molecular weight ( M e) of polyacrylates, as compared to polydienes, leads to “disappointing” mechanical performance as compared to styrenic TPEs. In this study, triblock copolymers composed of alkyl acrylates with different pendant groups and different glass transition temperatures ( T gs), i.e. 1-adamatyl acrylate (AdA) and tetrahydrofurfuryl acrylate (THFA), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Thermal characterization of the resulting polymers was performed using differential scanning calorimetry (DSC), and the T gs of both segments were observed for themore » block copolymers. This indication of microphase separation behavior was further demonstrated using atomic-force microscopy (AFM) and small angle X-ray scattering (SAXS). Dynamic mechanical analysis (DMA) showed that the softening temperature of the PAdA domains is 123 °C, which is higher than that of both styrenic TPEs and commercial acrylic based TPEs with poly(methyl methacrylate) (PMMA) hard block. Here, the resulting triblock copolymers also exhibited stress–strain behavior superior to that of conventional all acrylic-based TPEs composed of PMMA and poly( n-butyl acrylate) (PBA) made by controlled radical processes, while the tensile strength was lower than for products made by living anionic polymerization.« less

High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

NASA Astrophysics Data System (ADS)

Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

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.

PubMed

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.

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

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

Lee, Hoyoung; Tsouris, Vasilios; Lim, Yunho

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

Amplifying (Im)perfection: The Impact of Crystallinity in Discrete and Disperse Block Co-oligomers

PubMed Central

2017-01-01

Crystallinity is seldomly utilized as part of the microphase segregation process in ultralow-molecular-weight block copolymers. Here, we show the preparation of two types of discrete, semicrystalline block co-oligomers, comprising an amorphous oligodimethylsiloxane block and a crystalline oligo-l-lactic acid or oligomethylene block. The self-assembly of these discrete materials results in lamellar structures with unforeseen uniformity in the domain spacing. A systematic introduction of dispersity reveals the extreme sensitivity of the microphase segregation process toward chain length dispersity in the crystalline block. PMID:28994585

Amplifying (Im)perfection: The Impact of Crystallinity in Discrete and Disperse Block Co-oligomers.

PubMed

van Genabeek, Bas; Lamers, Brigitte A G; de Waal, Bas F M; van Son, Martin H C; Palmans, Anja R A; Meijer, E W

2017-10-25

Crystallinity is seldomly utilized as part of the microphase segregation process in ultralow-molecular-weight block copolymers. Here, we show the preparation of two types of discrete, semicrystalline block co-oligomers, comprising an amorphous oligodimethylsiloxane block and a crystalline oligo-l-lactic acid or oligomethylene block. The self-assembly of these discrete materials results in lamellar structures with unforeseen uniformity in the domain spacing. A systematic introduction of dispersity reveals the extreme sensitivity of the microphase segregation process toward chain length dispersity in the crystalline block.

Effect of rod length on the morphology of block copolymer/magnetic nanorod composites.

PubMed

Lo, Chieh-Tsung; Lin, Wei-Ting

2013-05-02

The organization of magnetic nanorods in microphase-separated diblock copolymers composed of poly(styrene-b-2-vinylpyridine) (PS-PVP) as a function of rod length and rod concentration was investigated using both transmission electron microscopy and small-angle X-ray scattering. Our results reveal that the nanorods were sequestered into the PVP domains, which is attributed to the preferential interaction between pyridine-tethered nanorods and PVP. Meanwhile, the addition of nanorods in PS-PVP caused chain stretching. To minimize the energy penalty, nanorods tended to align parallel to the interface between PS and PVP to increase the conformational entropy. As the length of nanorods increased, the increasing van der Waals interaction and magnetic interaction caused extensive rod aggregation, which suppressed the domain size of PVP and amplified the local compositional fluctuations. This creates conditions to induce disorder in the polymer morphology and nanorods undergo macrophase separation.

Flow-enhanced solution printing of all-polymer solar cells

DOE PAGES

Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; ...

2015-08-12

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a similar to 90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhancedmore » all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. However, we expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.« less

Flow-enhanced solution printing of all-polymer solar cells

PubMed Central

Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A.; Gu, Kevin; Gu, Xiaodan; Tee, Benjamin C. K.; Pang, Changhyun; Yan, Hongping; Zhao, Dahui; Toney, Michael F.; Mannsfeld, Stefan C. B.; Bao, Zhenan

2015-01-01

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility. PMID:26264528

A Laterally-Mobile Mixed Polymer/Polyelectrolyte Brush Undergoes a Macroscopic Phase Separation

NASA Astrophysics Data System (ADS)

Lee, Hoyoung; Park, Hae-Woong; Tsouris, Vasilios; Choi, Je; Mustafa, Rafid; Lim, Yunho; Meron, Mati; Lin, Binhua; Won, You-Yeon

2013-03-01

We studied mixed PEO and PDMAEMA brushes. The question we attempted to answer was: When the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Two different model mixed PEO/PDMAEMA brush systems were prepared: a mobile mixed brush by spreading a mixture of two diblock copolymers, PEO-PnBA and PDMAEMA-PnBA, onto the air-water interface, and an inseparable mixed brush using a PEO-PnBA-PDMAEMA triblock copolymer having respective brush molecular weights matched to those of the diblock copolymers. These two systems were investigated by surface pressure-area isotherm, X-ray reflectivity and AFM imaging measurements. The results suggest that the mobile mixed brush undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the inseparable system is only microscopically phase separated under comparable brush density conditions. We also conducted an SCF analysis of the phase behavior of the mixed brush system. This analysis further supported the experimental findings. The macroscopic phase separation observed in the mobile system is in contrast to the microphase separation behavior commonly observed in two-dimensional laterally-mobile small molecule mixtures.

Microphase Separation in Oil-Water Mixtures Containing Hydrophilic and Hydrophobic Ions

NASA Astrophysics Data System (ADS)

Tasios, Nikos; Samin, Sela; van Roij, René; Dijkstra, Marjolein

2017-11-01

We develop a lattice-based Monte Carlo simulation method for charged mixtures capable of treating dielectric heterogeneities. Using this method, we study oil-water mixtures containing an antagonistic salt, with hydrophilic cations and hydrophobic anions. Our simulations reveal several phases with a spatially modulated solvent composition, in which the ions partition between water-rich and water-poor regions according to their affinity. In addition to the recently observed lamellar phase, we find tubular and droplet phases, reminiscent of those found in block copolymers and surfactant systems. Interestingly, these structures stem from ion-mediated interactions, which allows for tuning of the phase behavior via the concentrations, the ionic properties, and the temperature.

Raman study of local ordering processes of solid n-alkanes

NASA Astrophysics Data System (ADS)

Hacura, A.; Zimnicka, B.; Wrzalik, R.

2016-02-01

The microphase separation of n-alkanes with different chain length was investigated by Raman spectroscopy for binary mixture rapidly quenched from the melt. The process was observed as a function of time. The first several minutes after solidification were crucial for the demixing process. For a few weeks old sample the orientational order parameters and were calculated based on the analysis of polarized spectra recorded in the area of the formed domains. The measured values are significantly greater than zero (from 0.17 to 0.32), which indicates the mutual parallel arrangement of the molecules in the domains composed of n-alkanes of the same chain length.

All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties

DOE PAGES

Lu, Wei; Wang, Yangyang; Wang, Weiyu; ...

2017-08-25

All acrylic-based thermoplastic elastomers (TPEs) offer potential alternatives to the widely-used styrenic TPEs. However, the high entanglement molecular weight ( M e) of polyacrylates, as compared to polydienes, leads to “disappointing” mechanical performance as compared to styrenic TPEs. In this study, triblock copolymers composed of alkyl acrylates with different pendant groups and different glass transition temperatures ( T gs), i.e. 1-adamatyl acrylate (AdA) and tetrahydrofurfuryl acrylate (THFA), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Thermal characterization of the resulting polymers was performed using differential scanning calorimetry (DSC), and the T gs of both segments were observed for themore » block copolymers. This indication of microphase separation behavior was further demonstrated using atomic-force microscopy (AFM) and small angle X-ray scattering (SAXS). Dynamic mechanical analysis (DMA) showed that the softening temperature of the PAdA domains is 123 °C, which is higher than that of both styrenic TPEs and commercial acrylic based TPEs with poly(methyl methacrylate) (PMMA) hard block. Here, the resulting triblock copolymers also exhibited stress–strain behavior superior to that of conventional all acrylic-based TPEs composed of PMMA and poly( n-butyl acrylate) (PBA) made by controlled radical processes, while the tensile strength was lower than for products made by living anionic polymerization.« less

Phase Behavior of Binary Blends of High Molecular Weight Diblock Copolymers with a Low Molecular Weight Triblock

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

Mickiewicz, Rafal A.; Ntoukas, Eleftherios; Avgeropoulos, Apostolos

2009-08-26

Binary blends of four different high molecular weight poly(styrene-b-isoprene) (SI) diblock copolymers with a lower molecular weight poly(styrene-b-isoprene-b-styrene) (SIS) triblock copolymer were prepared, and their morphology was characterized by transmission electron microscopy and ultra-small-angle X-ray scattering. All the neat block copolymers have nearly symmetric composition and exhibit the lamellar morphology. The SI diblock copolymers had number-average molecular weights, Mn, in the range 4.4 x 10{sup 5}--1.3 x 10{sup 6} g/mol and volume fractions of poly(styrene), {Phi}{sub PS}, in the range 0.43--0.49, and the SIS triblock had a molecular weight of Mn 6.2 x 10{sup 4} g/mol with {Phi}{sub PS} =more » 0.41. The high molecular weight diblock copolymers are very strongly segregating, with interaction parameter values, {chi}N, in the range 470--1410. A morphological phase diagram in the parameter space of molecular weight ratio (R = M{sub n}{sup diblock}/1/2M{sub n}{sup triblock}) and blend composition was constructed, with R values in the range between 14 and 43, which are higher than previously reported. The phase diagram revealed a large miscibility gap for the blends, with macrophase separation into two distinct types of microphase-separated domains for weight fractions of SI, w{sub SI} < 0.9, implying virtually no solubility of the much higher molecular weight diblocks in the lower molecular weight triblock. For certain blend compositions, above R 30, morphological transitions from the lamellar to cylindrical and bicontinuous structures were also observed.« less

Ordering of anisotropic nanoparticles in diblock copolymer lamellae: Simulations with dissipative particle dynamics and a molecular theory.

PubMed

Berezkin, Anatoly V; Kudryavtsev, Yaroslav V; Gorkunov, Maxim V; Osipov, Mikhail A

2017-04-14

Local distribution and orientation of anisotropic nanoparticles in microphase-separated symmetric diblock copolymers has been simulated using dissipative particle dynamics and analyzed with a molecular theory. It has been demonstrated that nanoparticles are characterized by a non-trivial orientational ordering in the lamellar phase due to their anisotropic interactions with isotropic monomer units. In the simulations, the maximum concentration and degree of ordering are attained for non-selective nanorods near the domain boundary. In this case, the nanorods have a certain tendency to align parallel to the interface in the boundary region and perpendicular to it inside the domains. Similar orientation ordering of nanoparticles located at the lamellar interface is predicted by the molecular theory which takes into account that the nanoparticles interact with monomer units via both isotropic and anisotropic potentials. Computer simulations enable one to study the effects of the nanorod concentration, length, stiffness, and selectivity of their interactions with the copolymer components on the phase stability and orientational order of nanoparticles. If the volume fraction of the nanorods is lower than 0.1, they have no effect on the copolymer transition from the disordered state into a lamellar microstructure. Increasing nanorod concentration or nanorod length results in clustering of the nanorods and eventually leads to a macrophase separation, whereas the copolymer preserves its lamellar morphology. Segregated nanorods of length close to the width of the diblock copolymer domains are stacked side by side into smectic layers that fill the domain space. Thus, spontaneous organization and orientation of nanorods leads to a spatial modulation of anisotropic composite properties which may be important for various applications.

Ordering of anisotropic nanoparticles in diblock copolymer lamellae: Simulations with dissipative particle dynamics and a molecular theory

NASA Astrophysics Data System (ADS)

Berezkin, Anatoly V.; Kudryavtsev, Yaroslav V.; Gorkunov, Maxim V.; Osipov, Mikhail A.

2017-04-01

Local distribution and orientation of anisotropic nanoparticles in microphase-separated symmetric diblock copolymers has been simulated using dissipative particle dynamics and analyzed with a molecular theory. It has been demonstrated that nanoparticles are characterized by a non-trivial orientational ordering in the lamellar phase due to their anisotropic interactions with isotropic monomer units. In the simulations, the maximum concentration and degree of ordering are attained for non-selective nanorods near the domain boundary. In this case, the nanorods have a certain tendency to align parallel to the interface in the boundary region and perpendicular to it inside the domains. Similar orientation ordering of nanoparticles located at the lamellar interface is predicted by the molecular theory which takes into account that the nanoparticles interact with monomer units via both isotropic and anisotropic potentials. Computer simulations enable one to study the effects of the nanorod concentration, length, stiffness, and selectivity of their interactions with the copolymer components on the phase stability and orientational order of nanoparticles. If the volume fraction of the nanorods is lower than 0.1, they have no effect on the copolymer transition from the disordered state into a lamellar microstructure. Increasing nanorod concentration or nanorod length results in clustering of the nanorods and eventually leads to a macrophase separation, whereas the copolymer preserves its lamellar morphology. Segregated nanorods of length close to the width of the diblock copolymer domains are stacked side by side into smectic layers that fill the domain space. Thus, spontaneous organization and orientation of nanorods leads to a spatial modulation of anisotropic composite properties which may be important for various applications.

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Studies on the effect of virtual crosslinking on the hydrolytic stability of novel aliphatic polyurethane ureas for blood contact applications.

PubMed

Thomas, V; Jayabalan, M

2001-07-01

The effect of virtual crosslinking on the hydrolytic stability of completely aliphatic novel poly(urethane ureas), HFL9-PU1 (hard-segment content 57.5%) and HFL13-PU2 (hard-segment content 67.9%) based on 4,4'-methylene bis(cyclohexyl isocyanate) (H(12)MDI)-hydroxy-terminated polybutadiene-1,6-hexamethylene diamine, was studied. Fourier transform infrared-attenuated total reflectance and wide-angle X-ray diffraction studies revealed hydrogen-bonding interaction and microphase separation and formation of crystallites by short- and long-range ordering in hard-segment domains. Three-dimensional networks from hydrogen bonding in the present polymers lead to virtually crosslinking and insolubility. These polymers were noncytotoxic to L929 fibroblast cells. The hemolytic potential is below the accepted limit. The studies on in vitro biostability in Ringer's solution, phosphate buffered saline, and papain enzyme revealed no weight loss. The infrared spectral studies revealed changes in the surface, especially on HFL9-PU1 aged in Ringer's solution and phosphate buffered saline, and no changes when aged in papain. The marginal changes noticed in tensile properties were attributed to the changes in degree of hydrogen bonding and associated rearrangement of molecular structure in the bulk. The results revealed that the lesser the crosslinking in virgin polymer, the higher the crosslinking in aged polymer and vice versa. Increased crosslinking during aging provided increased tensile properties in the aged polymer over the virgin polymer and vice versa. For comparison, an aliphatic polyetherurethane urea (HFL16-PU3) was also synthesized using poly(oxy tetra methylene glycol) in addition to the above reactants. Though both HFL9-PU1 and HFL16-PU3 contained the same hard-segment content, the aged sample of the latter showed decreased tensile properties with increased crosslinking during aging in contrast to the former. This was attributed to less microphase separation in the virgin HFL16-PU3 polymer.

Bio-Organic Nanotechnology: Using Proteins and Synthetic Polymers for Nanoscale Devices

NASA Technical Reports Server (NTRS)

Molnar, Linda K.; Xu, Ting; Trent, Jonathan D.; Russell, Thomas P.

2003-01-01

While the ability of proteins to self-assemble makes them powerful tools in nanotechnology, in biological systems protein-based structures ultimately depend on the context in which they form. We combine the self-assembling properties of synthetic diblock copolymers and proteins to construct intricately ordered, three-dimensional polymer protein structures with the ultimate goal of forming nano-scale devices. This hybrid approach takes advantage of the capabilities of organic polymer chemistry to build ordered structures and the capabilities of genetic engineering to create proteins that are selective for inorganic or organic substrates. Here, microphase-separated block copolymers coupled with genetically engineered heat shock proteins are used to produce nano-scale patterning that maximizes the potential for both increased structural complexity and integrity.

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

Y Hu; D Samanta; S Parelkar

Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylenemore » oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.« less

ABC triblock copolymer vesicles with mesh-like morphology.

PubMed

Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

2011-01-25

Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

Apertureless near-field vibrational imaging of block-copolymer nanostructures with ultrahigh spatial resolution.

PubMed

Raschke, Markus B; Molina, Leopoldo; Elsaesser, Thomas; Kim, Dong Ha; Knoll, Wolfgang; Hinrichs, Karsten

2005-10-14

Nanodomains formed by microphase separation in thin films of the diblock copolymers poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) and poly(styrene-b-ethyleneoxide) (PS-b-PEO) were imaged by means of infrared scattering-type near-field microscopy. When probing at 3.39 mum (2950 cm(-1)), contrast is obtained due to spectral differences between the C--H stretching vibrational resonances of the respective polymer constituents. An all-optical spatial resolution better than 10 nm was achieved, which corresponds to a sensitivity of just several thousand C--H groups facilitated by the local-field enhancement at the sharp metallic probe tips. The results demonstrate that infrared spectroscopy with access to intramolecular dimensions is within reach.

Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces.

PubMed

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.

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Cell adhesion on nanotopography

NASA Astrophysics Data System (ADS)

Tsai, Irene; Kimura, Masahiro; Stockton, Rebecca; Jacobson, Bruce; Russell, Thomas

2003-03-01

Cell adhesion, a key element in understanding the cell-biomaterial interactions, underpins proper cell growth, function and survival. Understanding the parameters influencing cell adhesion is critical for applications in biosensors, implants and bioreactors. A gradient surface is used to study the effect of the surface topography on cell adhesion. A gradient surface is generated by block copolymer and homopolymer blends. The two homopolymers will phase separate on the micron scale and gradually decrease to nano-scale by the microphase separation of the diblock. Gradient surfaces offer a unique opportunity to probe lateral variations in the topography and interactions. Using thin films of mixtures of diblock copolymers of PS-b-MMA with PS and PMMA homopolymers, where the concentration of the PS-b-MMA varies across the surface, a gradient in the size scale of the morphology, from the nanoscopic to microscopic, was produced. By UV exposure, the variation in morphology translated into a variation in topography. The extent of cell spreading and cytoskeleton formation was investigated and marked dependence on the length scale of the surface topography was found.

Block Copolymers: Synthesis and Applications in Nanotechnology

NASA Astrophysics Data System (ADS)

Lou, Qin

This study is focused on the synthesis and study of (block) copolymers using reversible deactivation radical polymerizations (RDRPs), including atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, two primary areas of study are undertaken: (1) a proof-of-concept application of lithographic block copolymers, and (2) the mechanistic study of the deposition of titania into block copolymer templates for the production of well-ordered titania nanostructures. Block copolymers have the ability to undergo microphase separation, with an average size of each microphase ranging from tens to hundreds of nanometers. As such, block copolymers have been widely considered for nanotechnological applications over the past two decades. The development of materials for various nanotechnologies has become an increasingly studied area as improvements in many applications, such as those found in the semiconductor and photovoltaic industries are constantly being sought. Significant growth in developments of new synthetic methods ( i.e. RDRPs) has allowed the production of block copolymers with molecular (and sometimes atomic) definition. In turn, this has greatly expanded the use of block copolymers in nanotechnology. Herein, we describe the synthesis of statistical and block copolymers of 193 nm photolithography methacrylate and acrylate resist monomers with norbornyl and adamantyl moieties using RAFT polymerization.. For these resist (block) copolymers, the phase separation behaviors were examined by atomic force microscopy (AFM). End groups were removed from the polymers to avoid complications during the photolithography since RAFT end groups absorb visible light. Poly(glycidyl methacrylate-block-polystyrene) (PGMA-b-PS) was synthesize by ATRP and demonstrated that this block copolymer acts as both a lithographic UV (365 nm) photoresist and a self-assembly material. The PGMA segments can undergo cationic ring-opening crosslinking and can act as a negative-tone photoresist. The PGMA-b-PS thin films were also studied for phase separation with ˜25 nm patterns using transmission electron microscopy (TEM). Poly(styrene-block-4-vinyl pyridine) (PS-b-P4VP) block copolymer thin films are shown to form perpendicular cylinder phase separated structures, and these may be used to template the formation of ordered titania nanostructures with sub-50 nm diameters on either silicon or indium tin oxide (ITO) substrates. A study of the mechanism of TiO2 formation within the P4VP cylinder phase was developed and tested. It was found that the titania nanostructure morphology is affected by pH and deposition temperatures, and successful deposition required the cross-linking of the P4VP phase in order to obtain individual nanostructures.

Theory of domain patterns in systems with long-range interactions of Coulomb type.

PubMed

Muratov, C B

2002-12-01

We develop a theory of the domain patterns in systems with competing short-range attractive interactions and long-range repulsive Coulomb interactions. We take an energetic approach, in which patterns are considered as critical points of a mean-field free energy functional. Close to the microphase separation transition, this functional takes on a universal form, allowing us to treat a number of diverse physical situations within a unified framework. We use asymptotic analysis to study domain patterns with sharp interfaces. We derive an interfacial representation of the pattern's free energy which remains valid in the fluctuating system, with a suitable renormalization of the Coulomb interaction's coupling constant. We also derive integro-differential equations describing stationary domain patterns of arbitrary shapes and their thermodynamic stability, coming from the first and second variations of the interfacial free energy. We show that the length scale of a stable domain pattern must obey a certain scaling law with the strength of the Coulomb interaction. We analyzed the existence and stability of localized (spots, stripes, annuli) and periodic (lamellar, hexagonal) patterns in two dimensions. We show that these patterns are metastable in certain ranges of the parameters and that they can undergo morphological instabilities leading to the formation of more complex patterns. We discuss nucleation of the domain patterns by thermal fluctuations and pattern formation scenarios for various thermal quenches. We argue that self-induced disorder is an intrinsic property of the domain patterns in the systems under consideration.

Co-crystallization phase transformations in all π-conjugated block copolymers with different main-chain moieties.

PubMed

Lee, Yi-Huan; Chen, Wei-Chih; Yang, Yi-Lung; Chiang, Chi-Ju; Yokozawa, Tsutomu; Dai, Chi-An

2014-05-21

Driven by molecular affinity and balance in the crystallization kinetics, the ability to co-crystallize dissimilar yet self-crystallizable blocks of a block copolymer (BCP) into a uniform domain may strongly affect its phase diagram. In this study, we synthesize a new series of crystalline and monodisperse all-π-conjugated poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-(2-ethylhexyl)thiophene) (PPP-P3EHT) BCPs and investigate this multi-crystallization effect. Despite vastly different side-chain and main-chain structures, PPP and P3EHT blocks are able to co-crystallize into a single uniform domain comprising PPP and P3EHT main-chains with mutually interdigitated side-chains spaced in-between. With increasing P3EHT fraction, PPP-P3EHTs undergo sequential phase transitions and form hierarchical superstructures including predominately PPP nanofibrils, co-crystalline nanofibrils, a bilayer co-crystalline/pure P3EHT lamellar structure, a microphase-separated bilayer PPP-P3EHT lamellar structure, and finally P3EHT nanofibrils. In particular, the presence of the new co-crystalline lamellar structure is the manifestation of the interaction balance between self-crystallization and co-crystallization of the dissimilar polymers on the resulting nanostructure of the BCP. The current study demonstrates the co-crystallization nature of all-conjugated BCPs with different main-chain moieties and may provide new guidelines for the organization of π-conjugated BCPs for future optoelectronic applications.

Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration

NASA Astrophysics Data System (ADS)

Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan; Liang, Heyi; Rosenthal, Martin; Sztucki, Michael; Clair, Charles; Magonov, Sergei; Ivanov, Dimitri A.; Dobrynin, Andrey V.; Sheiko, Sergei S.

2018-03-01

Active camouflage is widely recognized as a soft-tissue feature, and yet the ability to integrate adaptive coloration and tissuelike mechanical properties into synthetic materials remains elusive. We provide a solution to this problem by uniting these functions in moldable elastomers through the self-assembly of linear-bottlebrush-linear triblock copolymers. Microphase separation of the architecturally distinct blocks results in physically cross-linked networks that display vibrant color, extreme softness, and intense strain stiffening on par with that of skin tissue. Each of these functional properties is regulated by the structure of one macromolecule, without the need for chemical cross-linking or additives. These materials remain stable under conditions characteristic of internal bodily environments and under ambient conditions, neither swelling in bodily fluids nor drying when exposed to air.

Fabrication of 3-D nanodimensioned electric double layer capacitor structures using block copolymer templates.

PubMed

Rasappa, Sozaraj; Borah, Dipu; Senthamaraikannan, Ramsankar; Faulkner, Colm C; Holmes, Justin D; Morris, Michael A

2014-07-01

The need for materials for high energy storage has led to very significant research in supercapacitor systems. These can exhibit electrical double layer phenomena and capacitances up to hundreds of F/g. Here, we demonstrate a new supercapacitor fabrication methodology based around the microphase separation of PS-b-PMMA which has been used to prepare copper nanoelectrodes of dimension -13 nm. These structures provide excellent capacitive performance with a maximum specific capacitance of -836 F/g for a current density of 8.06 A/g at a discharge current as high as 75 mA. The excellent performance is due to a high surface area: volume ratio. We suggest that this highly novel, easily fabricated structure might have a number of important applications.

Functional and Multifunctional Polymers: Materials for Smart Structures

NASA Technical Reports Server (NTRS)

Arnold, S.; Pratt, L. M.; Li, J.; Wuagaman, M.; Khan, I. M.

1996-01-01

The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three examples of multifunctional polymers developed in our labs will be reported. The first class of multifunctional polymers are the microphase separated mixed (ionic and electronic) conducting or MIEC block copolymers. The second class being developed in our labs are the biocompatible conductive materials and the conductive fluids. The final class may be considered microwave active smart polymers.

Ion transport mechanisms in lamellar phases of salt-doped PS-PEO block copolymer electrolytes.

PubMed

Sethuraman, Vaidyanathan; Mogurampelly, Santosh; Ganesan, Venkat

2017-11-01

We use a multiscale simulation strategy to elucidate, at an atomistic level, the mechanisms underlying ion transport in the lamellar phase of polystyrene-polyethylene oxide (PS-PEO) block copolymer (BCP) electrolytes doped with LiPF 6 salts. Explicitly, we compare the results obtained for ion transport in the microphase separated block copolymer melts to those for salt-doped PEO homopolymer melts. In addition, we also present results for dynamics of the ions individually in the PEO and PS domains of the BCP melt, and locally as a function of the distance from the lamellar interfaces. When compared to the PEO homopolymer melt, ions were found to exhibit slower dynamics in both the block copolymer (overall) and in the PEO phase of the BCP melt. Such results are shown to arise from the effects of slower polymer segmental dynamics in the BCP melt and the coordination characteristics of the ions. Polymer backbone-ion residence times analyzed as a function of distance from the interface indicate that ions have a larger residence time near the interface compared to that near the bulk of lamella, and demonstrates the influence of the glassy PS blocks and microphase segregation on the ion transport properties. Ion transport mechanisms in BCP melts reveal that there exist five distinct mechanisms for ion transport along the backbone of the chain and exhibit qualitative differences from the behavior in homopolymer melts. We also present results as a function of salt concentration which show that the mean-squared displacements of the ions decrease with increasing salt concentration, and that the ion residence times near the polymer backbone increase with increasing salt concentration.

Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold

DOE PAGES

Ahn, Suk-kyun; Carrillo, Jan-Michael Y.; Keum, Jong K.; ...

2017-04-07

The ability to widely tune the design of macromolecular bottlebrushes provides access to self-assembled nanostructures formed by microphase segregation in melt, thin film and solution that depart from structures adopted by simple linear copolymers. A series of random bottlebrush copolymers containing poly(3-hexylthiophene) (P3HT) and poly(D,L-lactide) (PLA) side chains grafted on a poly(norbornene) backbone were synthesized via ring-opening metathesis polymerization (ROMP) using the grafting through approach. P3HT side chains induce a physical aggregation of the bottlebrush copolymers upon solvent removal by vacuum drying, primarily driven by attractive π–π interactions; however, the amount of aggregation can be controlled by adjusting side chainmore » composition or by adding linear P3HT chains to the bottlebrush copolymers. Coarse-grained molecular dynamics simulations reveal that linear P3HT chains preferentially associate with P3HT side chains of bottlebrush copolymers, which tends to reduce the aggregation. The nanoscale morphology of microphase segregated thin films created by casting P3HT–PLA random bottlebrush copolymers is highly dependent on the composition of P3HT and PLA side chains, while domain spacing of nanostructures is mainly determined by the length of the side chains. The selective removal of PLA side chains under alkaline conditions generates nanoporous P3HT structures that can be tuned by manipulating molecular design of the bottlebrush scaffold, which is affected by molecular weight and grafting density of the side chains, and their sequence. Furthermore, the ability to exploit the unusual architecture of bottlebrushes to fabricate tunable nanoporous P3HT thin film structures may be a useful way to design templates for optoelectronic applications or membranes for separations.« less

Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold

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

Ahn, Suk-kyun; Carrillo, Jan-Michael Y.; Keum, Jong K.

The ability to widely tune the design of macromolecular bottlebrushes provides access to self-assembled nanostructures formed by microphase segregation in melt, thin film and solution that depart from structures adopted by simple linear copolymers. A series of random bottlebrush copolymers containing poly(3-hexylthiophene) (P3HT) and poly(D,L-lactide) (PLA) side chains grafted on a poly(norbornene) backbone were synthesized via ring-opening metathesis polymerization (ROMP) using the grafting through approach. P3HT side chains induce a physical aggregation of the bottlebrush copolymers upon solvent removal by vacuum drying, primarily driven by attractive π–π interactions; however, the amount of aggregation can be controlled by adjusting side chainmore » composition or by adding linear P3HT chains to the bottlebrush copolymers. Coarse-grained molecular dynamics simulations reveal that linear P3HT chains preferentially associate with P3HT side chains of bottlebrush copolymers, which tends to reduce the aggregation. The nanoscale morphology of microphase segregated thin films created by casting P3HT–PLA random bottlebrush copolymers is highly dependent on the composition of P3HT and PLA side chains, while domain spacing of nanostructures is mainly determined by the length of the side chains. The selective removal of PLA side chains under alkaline conditions generates nanoporous P3HT structures that can be tuned by manipulating molecular design of the bottlebrush scaffold, which is affected by molecular weight and grafting density of the side chains, and their sequence. Furthermore, the ability to exploit the unusual architecture of bottlebrushes to fabricate tunable nanoporous P3HT thin film structures may be a useful way to design templates for optoelectronic applications or membranes for separations.« less

Incorporating fluorinated moieties in fully conjugated donor-acceptor block copolymers

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Wang, Qing; Gomez, Enrique D.

Fully conjugated donor-acceptor block copolymers are promising candidates for photovoltaics due to their ability to microphase separate at length scales commensurate with exciton diffusion lengths. These materials can also serve as model systems to study the relationship between molecular structure, microstructure, and optoelectronic properties of conjugated polymers. The development of new donor-acceptor block copolymers relies on the manipulation of the chemical structure to fine tune properties and improve overall performance when employed in photovoltaic devices. To this end, we have demonstrated the incorporation of fluorinated moieties in conjugated block copolymers. The introduction of fluorine, a strong electron withdrawing element, is known to influence phase separation and the bandgap, and as a result, optoelectronic properties. Fluorine was introduced to the acceptor block of poly(3-hexylthiophene-2,5-diyl)-block-poly((9,9-bis(2-octyl)fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5 ',5?-diyl) (P3HT- b-PFTBT). PFTBTs were prepared with di-fluorinated and mono-fluorinated TBT. We find that fluorination impacts the bandgap, morphology and performance in devices.

Development of mass production technology for block copolymer lithographic materials

NASA Astrophysics Data System (ADS)

Himi, Toshiyuki; Matsuki, Ryota; Kosaka, Terumasa; Ogaki, Ryosuke; Kawaguchi, Yukio; Shimizu, Tetsuo

2017-03-01

We have successfully synthesized various and over wide range molecular weight block copolymers (BCPs): these are polystyrene(PS)-polymethylmethacrylate(PMMA) as general components and poly(4-trimethylsilylstyrene)(PTMSS)- poly(4-hydroxystyrene)(PHS) system as very strong segregated components (high chi) and multiblock type of those copolymers which form the microphase-separated structure pattern using living anionic polymerizing method by which the size of polymer can be precisely controlled. In addition, we were able to observe alternating lamellar and cylinder structures which were formed by our various BCPs using small angle X-ray scattering (SAXS). Moreover, we have successfully developed new apparatus for high volume manufacturing including our original technologies such as purification of monomer, improvement of wetted surface, and mechanical technology for high vacuum. And we have successfully synthesized all the BCPs with narrow molecular weight distribution (PDI <1.1) with large-scale apparatus.

Effect of matrix chemical heterogeneity on effective filler interactions in model polymer nanocomposites

NASA Astrophysics Data System (ADS)

Hall, Lisa; Schweizer, Kenneth

2010-03-01

The microscopic Polymer Reference Interaction Site Model theory has been applied to spherical and rodlike fillers dissolved in three types of chemically heterogeneous polymer melts: alternating AB copolymer, random AB copolymers, and an equimolar blend of two homopolymers. In each case, one monomer species adsorbs more strongly on the filler mimicking a specific attraction, while all inter-monomer potentials are hard core which precludes macrophase or microphase separation. Qualitative differences in the filler potential-of-mean force are predicted relative to the homopolymer case. The adsorbed bound layer for alternating copolymers exhibits a spatial moduluation or layering effect but is otherwise similar to that of the homopolymer system. Random copolymers and the polymer blend mediate a novel strong, long-range bridging interaction between fillers at moderate to high adsorption strengths. The bridging strength is a non-monotonic function of random copolymer composition, reflecting subtle competing enthalpic and entropic considerations.

Response of cells on surface-induced nanopatterns: fibroblasts and mesenchymal progenitor cells.

PubMed

Khor, Hwei Ling; Kuan, Yujun; Kukula, Hildegard; Tamada, Kaoru; Knoll, Wolfgang; Moeller, Martin; Hutmacher, Dietmar W

2007-05-01

Ultrathin films of a poly(styrene)-block-poly(2-vinylpyrindine) diblock copolymer (PS-b-P2VP) and poly(styrene)-block-poly(4-vinylpyrindine) diblock copolymer (PS-b-P4VP) were used to form surface-induced nanopattern (SINPAT) on mica. Surface interaction controlled microphase separation led to the formation of chemically heterogeneous surface nanopatterns on dry ultrathin films. Two distinct nanopatterned surfaces, namely, wormlike and dotlike patterns, were used to investigate the influence of topography in the nanometer range on cell adhesion, proliferation, and migration. Atomic force microscopy was used to confirm that SINPAT was stable under cell culture conditions. Fibroblasts and mesenchymal progenitor cells were cultured on the nanopatterned surfaces. Phase contrast and confocal laser microscopy showed that fibroblasts and mesenchymal progenitor cells preferred the densely spaced wormlike patterns. Atomic force microscopy showed that the cells remodelled the extracellular matrix differently as they migrate over the two distinctly different nanopatterns.

Control of Mechanical Properties of Thermoplastic Polyurethane Elastomers by Restriction of Crystallization of Soft Segment

PubMed Central

Kojio, Ken; Furukawa, Mutsuhisa; Nonaka, Yoshiteru; Nakamura, Sadaharu

2010-01-01

Mechanical properties of thermoplastic polyurethane elastomers based on either polyether or polycarbonate (PC)-glycols, 4,4’-dipheylmethane diisocyanate (1,1’-methylenebis(4-isocyanatobenzene)), 1,4-butanediol, were controlled by restriction of crystallization of polymer glycols. For the polyether glycol based-polyurethane elastomers (PUEs), poly(oxytetramethylene) glycol (PTMG), and PTMG incorporating dimethyl groups (PTG-X) and methyl side groups (PTG-L) were employed as a polymer glycol. For the PC-glycol, the randomly copolymerized PC-glycols with hexamethylene (C6) and tetramethylene (C4) units between carbonate groups with various composition ratios (C4/C6 = 0/100, 50/50, 70/30 and 90/10) were employed. The degree of microphase separation and mechanical properties of both the PUEs were investigated using differential scanning calorimetry, dynamic viscoelastic property measurements and tensile testing. Mechanical properties could be controlled by changing the molar ratio of two different monomer components. PMID:28883371

Surface immobilization of heparin on functional polyisobutylene-based thermoplastic elastomer as a potential artificial vascular graft

NASA Astrophysics Data System (ADS)

Wu, Yi-Bo; Li, Kang; Xiang, Dong; Zhang, Min; Yang, Dan; Zhang, Jin-Han; Mao, Jing; Wang, Hao; Guo, Wen-Li

2018-07-01

Polyisobutylene-based thermoplastic elastomer (TPE) is a new soft biomaterial. Hydroxyl functional dendritic polyisobutylene-based TPEs (arb-SIBS-OH), which satisfy the design requirements for small-diameter vascular substitutes, were synthesized by controlled carbocationic polymerization. Creep property, which is the destructive weakness of polyisobutylene-based TPEs, was significantly improved with the formation of a "double network" promoted by branched structure and microphase separation. Compatibility of arb-SIBS-OH with rabbit blood was markedly enhanced by modifying heparin grafted from these hydroxyl functional groups. Application of "click chemistry" to immobilize heparin on arb-SIBS-OH surface was apparently effective in enhancing the bioactivity of heparin. Immobilized heparin, which directly bonded by ester bonds, was more likely to form multi-point binding on arb-SIBS-OH surface. This process hindered the accessibility of the heparin active sequence to antithrombin.

Crystallization features of normal alkanes in confined geometry.

PubMed

Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

2014-01-21

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

New approach for producing chemical templates over large area by Molecular Transfer Printing

NASA Astrophysics Data System (ADS)

Inoue, Takejiro; Janes, Dustin; Ren, Jiaxing; Willson, Grant; Ellison, Christopher; Nealey, Paul

2014-03-01

Fabrication of well-defined chemically patterned surfaces is crucially important to the development of next generation microprocessors, hard disk memory devices, photonic/plasmonic devices, separation membranes, and biological microarrays. One promising patterning method in these fields is Molecular Transfer Printing (MTP), which replicates chemical patterns with feature dimensions of the order of 10nm utilizing a master template defined by the microphase separated domains of a block copolymer thin film. The total transfer printing area achievable by MTP has so far been limited by the contact area between two rigid substrates. Therefore, strategies to make conformal contact between substrates could be practically useful because a single lithographically-defined starting pattern could be used to fabricate many replicates by a low-cost process. Here we show a new approach that utilizes a chemically deposited SiN layer and a liquid conformal layer to enable transfer printing of chemical patterns upon thermal annealing over large, continuous areas. We anticipate that our process could be integrated into Step and Flash Imprint Lithography (SFIL) tools to achieve conformal layer thicknesses thin and uniform enough to permit pattern transfer through a dry-etch protocol.

On the comparisons between dissipative particle dynamics simulations and self-consistent field calculations of diblock copolymer microphase separation

NASA Astrophysics Data System (ADS)

Sandhu, Paramvir; Zong, Jing; Yang, Delian; Wang, Qiang

2013-05-01

To highlight the importance of quantitative and parameter-fitting-free comparisons among different models/methods, we revisited the comparisons made by Groot and Madden [J. Chem. Phys. 108, 8713 (1998), 10.1063/1.476300] and Chen et al. [J. Chem. Phys. 122, 104907 (2005), 10.1063/1.1860351] between their dissipative particle dynamics (DPD) simulations of the DPD model and the self-consistent field (SCF) calculations of the "standard" model done by Matsen and Bates [Macromolecules 29, 1091 (1996), 10.1021/ma951138i] for diblock copolymer (DBC) A-B melts. The small values of the invariant degree of polymerization used in the DPD simulations do not justify the use of the fluctuation theory of Fredrickson and Helfand [J. Chem. Phys. 87, 697 (1987), 10.1063/1.453566] by Groot and Madden, and their fitting between the DPD interaction parameters and the Flory-Huggins χ parameter in the "standard" model also has no rigorous basis. Even with their use of the fluctuation theory and the parameter-fitting, we do not find the "quantitative match" for the order-disorder transition of symmetric DBC claimed by Groot and Madden. For lamellar and cylindrical structures, we find that the system fluctuations/correlations decrease the bulk period and greatly suppress the large depletion of the total segmental density at the A-B interfaces as well as its oscillations in A- and B-domains predicted by our SCF calculations of the DPD model. At all values of the A-block volume fractions in the copolymer f (which are integer multiples of 0.1), our SCF calculations give the same sequence of phase transitions with varying χN as the "standard" model, where N denotes the number of segments on each DBC chain. All phase boundaries, however, are shifted to higher χN due to the finite interaction range in the DPD model, except at f = 0.1 (and 0.9), where χN at the transition between the disordered phase and the spheres arranged on a body-centered cubic lattice is lower due to N = 10 in the DPD model. Finally, in 11 of the total 20 cases (f-χN combinations) studied in the DPD simulations, a morphology different from the SCF prediction was obtained due to the differences between these two methods.

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.

Breaking the barriers of all-polymer solar cells: Solving electron transporter and morphology problems

NASA Astrophysics Data System (ADS)

Gavvalapalli, Nagarjuna

All-polymer solar cells (APSC) are a class of organic solar cells in which hole and electron transporting phases are made of conjugated polymers. Unlike polymer/fullerene solar cell, photoactive material of APSC can be designed to have hole and electron transporting polymers with complementary absorption range and proper frontier energy level offset. However, the highest reported PCE of APSC is 5 times less than that of polymer/fullerene solar cell. The low PCE of APSC is mainly due to: i) low charge separation efficiency; and ii) lack of optimal morphology to facilitate charge transfer and transport; and iii) lack of control over the exciton and charge transport in each phase. My research work is focused towards addressing these issues. The charge separation efficiency of APSC can be enhanced by designing novel electron transporting polymers with: i) broad absorption range; ii) high electron mobility; and iii) high dielectric constant. In addition to with the above parameters chemical and electronic structure of the repeating unit of conjugated polymer also plays a role in charge separation efficiency. So far only three classes of electron transporting polymers, CN substituted PPV, 2,1,3-benzothiadiazole derived polymers and rylene diimide derived polymers, are used in APSC. Thus to enhance the charge separation efficiency new classes of electron transporting polymers with the above characteristics need to be synthesized. I have developed a new straightforward synthetic strategy to rapidly generate new classes of electron transporting polymers with different chemical and electronic structure, broad absorption range, and high electron mobility from readily available electron deficient monomers. In APSCs due to low entropy of mixing, polymers tend to micro-phase segregate rather than forming the more useful nano-phase segregation. Optimizing the polymer blend morphology to obtain nano-phase segregation is specific to the system under study, time consuming, and not trivial. Thus to avoid micro-phase segregation, nanoparticles of hole and electron transporters are synthesized and blended. But the PCE of nanoparticle blends are far less than those of polymer blends. This is mainly due to the: i) lack of optimal assembly of nanoparticles to facilitate charge transfer and transport processes; and ii) lack of control over the exciton and charge transport properties within the nanoparticles. Polymer packing within the nanoparticle controls the optoelectronic and charge transport properties of the nanoparticle. In this work I have shown that the solvent used to synthesize nanoparticles plays a crucial role in determining the assembly of polymer chains inside the nanoparticle there by affecting its exciton and charge transport processes. To obtain the optimal morphology for better charge transfer and transport, we have also synthesized nanoparticles of different radius with surfactants of opposite charge. We propose that depending on the radius and/or Coulombic interactions these nanoparticles can be assembled into mineral structure-types that are useful for photovoltaic devices.

The influence of chain rigidity and the degree of sulfonation on the morphology of block copolymers as nano reactor

NASA Astrophysics Data System (ADS)

Hong, K.; Zhang, X.

2005-03-01

Polyelectrolyte block copolymer was used to form an ordered domain of ionic block as a ``nanoreactor'' due to its ability to bind oppositely charged metal ion, Zn^2+, Fe^2+ etc. The purpose of our research is to investigate the controllability of the size and morphology of domains (inorganic nano particles) by changing backbone stiffness, the charge density and the volume fraction of ionic block. Poly(styrene sulfonate) (PSS), which backbone is flexible, and poly(cyclohexadiene sulfonate) (PCHDS), which backbone is ``semiflexible'', were used as ionic blocks. We synthesized PtBS-PSS and PS-PCHDS with various degree of sulfonation and the volume fraction. Zinc oxide (ZnO) nano particles successfully formed in the ionic domain of microphase separated block copolymers. We used SANS to characterize the morphology of block copolymers and TEM for block copolymer containing ZnO nano particles. Our experimental results show that the chemistry of ``sulfonation'' of block copolymers can be successfully used to synthesize nano composite materials.

Block Copolymer-Templated Approach to Nanopatterned Metal-Organic Framework Films.

PubMed

Zhou, Meimei; Wu, Yi-Nan; Wu, Baozhen; Yin, Xianpeng; Gao, Ning; Li, Fengting; Li, Guangtao

2017-08-17

The fabrication of patterned metal-organic framework (MOF) films with precisely controlled nanoscale resolution has been a fundamental challenge in nanoscience and nanotechnology. In this study, nanopatterned MOF films were fabricated using a layer-by-layer (LBL) growth method on functional templates (such as a bicontinuous nanoporous membrane or a structure with highly long-range-ordered nanoscopic channels parallel to the underlying substrate) generated by the microphase separation of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymers. HKUST-1 can be directly deposited on the templates without any chemical modification because the pyridine groups in P2VP interact with metal ions via metal-BCP complexes. As a result, nanopatterned HKUST-1 films with feature sizes below 50 nm and controllable thicknesses can be fabricated by controlling the number of LBL growth cycles. The proposed fabrication method further extends the applications of MOFs in various fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Ertem, S. Piril; Caire, Benjamin R.; Tsai, Tsung-Han

Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion-exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase-separated morphologies with well-defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ionmore » exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br2 at 90 8C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. Xray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non-ionic domains in a connected ionic phase.« less

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

NASA Astrophysics Data System (ADS)

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

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

Molecular and morphological characterization of midblock-sulfonated styrenic triblock copolymers

DOE PAGES

Mineart, Kenneth P.; Ryan, Justin J.; Lee, Byeongdu; ...

2017-01-11

Midblock-sulfonated triblock copolymers afford a desirable opportunity to generate network-forming amphiphilic materials that are suitable for use in a wide range of emerging technologies as fuel-cell, water-desalination, ion-exchange, photovoltaic, or electroactive membranes. Employing a previously reported synthetic strategy wherein poly( p- tert-butylstyrene) remains unreactive, we have selectively sulfonated the styrenic midblock of a poly( p- tert-butylstyrene- b-styrene- b- p- tert- butylstyrene) (TST) triblock copolymer to different extents. Comparison of the resulting sulfonated copolymers with results from our prior study provides favorable quantitative agreement and suggests that a shortened reaction time is advantageous. An ongoing challenge regarding the morphological development ofmore » charged block copolymers is the competition between microphase separation of the incompatible blocks and physical cross-linking of ionic clusters, with the latter often hindering the former. Here, we expose the sulfonated TST copolymers to solvent-vapor annealing to promote nanostructural refinement. Furthermore, the effect of such annealing on morphological characteristics, as well as on molecular free volume, is explored.« less

NMR study on the network structure of a mixed gel of kappa and iota carrageenans.

PubMed

Hu, Bingjie; Du, Lei; Matsukawa, Shingo

2016-10-05

The temperature dependencies of the (1)H T2 and diffusion coefficient (D) of a mixed solution of kappa-carrageenan and iota-carrageenan were measured by NMR. Rheological and NMR measurements suggested an exponential formation of rigid aggregates of kappa-carrageenan and a gradual formation of fine aggregates of iota-carrageenan during two step increases of G'. The results also suggested that longer carrageenan chains are preferentially involved in aggregation, thus resulting in a decrease in the average Mw of solute carrageenans. The results of diffusion measurements for poly(ethylene oxide) (PEO) suggested that kappa-carrageenan formed thick aggregates that decreased hindrance to PEO diffusion by decreasing the solute kappa-carrageenan concentration in the voids of the aggregated chains, and that iota-carrageenan formed fine aggregates that decreased the solute iota-carrageenan concentration less. DPEO in a mixed solution of kappa-carrageenan and iota-carrageenan suggested two possibilities for the microscopic network structure: an interpenetrating network structure, or micro-phase separation. Copyright © 2016. Published by Elsevier Ltd.

Fluids Density Functional Theory of Salt-Doped Block Copolymers

NASA Astrophysics Data System (ADS)

Brown, Jonathan R.; Hall, Lisa M.

Block copolymers have attracted a great deal of recent interest as potential non-flammable, solid-state, electrolyte materials for batteries or other charge carrying applications. The microphase separation in block copolymers combines the properties of a conductive (though mechanically soft) polymer with a mechanically robust (though non-conductive) polymer. We use fluids density functional theory (fDFT) to study the phase behavior of salt-doped block copolymers. Because the salt prefers to preferentially solvate into the conductive phase, salt doping effectively enhances the segregation strength between the two polymer types. We consider the effects of this preferential solvation and of charge correlations by separately modeling the ion-rich phase, without bonding, using the Ornstein-Zernike equation and the hypernetted-chain closure. We use the correlations from this subsystem in the inhomogeneous fDFT calculations. Initial addition of salt increases the domain spacing and sharpens the interfacial region, but for high salt loadings the interface can broaden. Addition of salt can also drive a system with a low copolymer segregation strength to order by first passing through a two phase regime with a salt-rich ordered phase and a salt-poor disordered phase. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0014209.

Mammalian Cell Interactions with Nanophase Materials

DTIC Science & Technology

2005-01-01

alumina , titania and hydroxylapatite) as well as on composites of these ceramics with either poly(L-lactic) acid or poly(methyl) methacrylate. Most...osteoblasts on flat, nanophase (versus microphase/conventional) ceramics ( alumina , titania and hydroxylapatite) as a function of decreasing ceramic grain size...acid (PLA) and nanophase (but not on polymer/conventional) ceramics ( alumina , titania and hydroxylapatite) composites [4]. Specifically, osteoblast

Analysis of transitional separation bubbles on infinite swept wings

NASA Technical Reports Server (NTRS)

Davis, R. L.; Carter, J. E.

1986-01-01

A previously developed two-dimensional local inviscid-viscous interaction technique for the analysis of airfoil transitional separation bubbles, ALESEP (Airfoil Leading Edge Separation), has been extended for the calculation of transitional separation bubbles over infinite swept wings. As part of this effort, Roberts' empirical correlation, which is interpreted as a separated flow empirical extension of Mack's stability theory for attached flows, has been incorporated into the ALESEP procedure for the prediction of the transition location within the separation bubble. In addition, the viscous procedure used in the ALESEP techniques has been modified to allow for wall suction. A series of two-dimensional calculations is presented as a verification of the prediction capability of the interaction techniques with the Roberts' transition model. Numerical tests have shown that this two-dimensional natural transition correlation may also be applied to transitional separation bubbles over infinite swept wings. Results of the interaction procedure are compared with Horton's detailed experimental data for separated flow over a swept plate which demonstrates the accuracy of the present technique. Wall suction has been applied to a similar interaction calculation to demonstrate its effect on the separation bubble. The principal conclusion of this paper is that the prediction of transitional separation bubbles over two-dimensional or infinite swept geometries is now possible using the present interacting boundary layer approach.

Roll-to-Roll printed large-area all-polymer solar cells with 5% efficiency based on a low crystallinity conjugated polymer blend

NASA Astrophysics Data System (ADS)

Gu, Xiaodan; Zhou, Yan; Gu, Kevin; Kurosawa, Tadanori; Yan, Hongping; Wang, Cheng; Toney, Micheal; Bao, Zhenan

The challenge of continuous printing in high efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution coated all-polymer bulk heterojunction (BHJ) solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, our results showed that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. We were able to continuously roll-to-roll slot die print large area all-polymer solar cells with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R coated active layer organic materials on flexible substrate. DOE BRIDGE sunshot program. Office of Naval Research.

Time-resolved atomic force microscopy imaging studies of asymmetric PS-b-PMMA ultrathin films: Dislocation and disclination transformations, defect mobility, and evolution of nanoscale morphology

NASA Astrophysics Data System (ADS)

Hahm, J.; Sibener, S. J.

2001-03-01

Time-sequenced atomic force microscopy (AFM) studies of ultrathin films of cylinder-forming polystyrene-block-polymethylmethacrylate (PS-b-PMMA) copolymer are presented which delineate thin film mobility kinetics and the morphological changes which occur in microphase-separated films as a function of annealing temperature. Of particular interest are defect mobilities in the single layer (L thick) region, as well as the interfacial morphological changes which occur between L thick and adjacent 3L/2 thick layers, i.e., structural changes which occur during multilayer evolution. These measurements have revealed the dominant pathways by which disclinations and dislocations transform, annihilate, and topologically evolve during thermal annealing of such films. Mathematical combining equations are given to better explain such defect transformations and show the topological outcomes which result from defect-defect encounters. We also report a collective, Arrhenius-type flow of defects in localized L thick regions of the film; these are characterized by an activation energy of 377 kJ/mol. These measurements represent the first direct investigation of time-lapse interfacial morphological changes including associated defect evolution pathways for polymeric ultrathin films. Such observations will facilitate a more thorough and predictive understanding of diblock copolymer thin film dynamics, which in turn will further enable the utilization of these nanoscale phase-separated materials in a range of physical and chemical applications.

Roll-to-Roll Printed Large-Area All-Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

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

Gu, Xiaodan; Zhou, Yan; Gu, Kevin

The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers.more » This particular methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm 2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.« less

Roll-to-Roll Printed Large-Area All-Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

DOE PAGES

Gu, Xiaodan; Zhou, Yan; Gu, Kevin; ...

2017-03-07

The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers.more » This particular methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm 2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.« less

Effect of CMC Molecular Weight on Acid-Induced Gelation of Heated WPI-CMC Soluble Complex.

PubMed

Huan, Yan; Zhang, Sha; Vardhanabhuti, Bongkosh

2016-02-01

Acid-induced gelation properties of heated whey protein isolate (WPI) and carboxymethylcellulose (CMC) soluble complex were investigated as a function of CMC molecular weight (270, 680, and 750 kDa) and concentrations (0% to 0.125%). Heated WPI-CMC soluble complex with 6% protein was made by heating biopolymers together at pH 7.0 and 85 °C for 30 min and diluted to 5% protein before acid-induced gelation. Acid-induced gel formed from heated WPI-CMC complexes exhibited increased hardness and decreased water holding capacity with increasing CMC concentrations but gel strength decreased at higher CMC content. The highest gel strength was observed with CMC 750 k at 0.05%. Gels with low CMC concentration showed homogenous microstructure which was independent of CMC molecular weight, while increasing CMC concentration led to microphase separation with higher CMC molecular weight showing more extensive phase separation. When heated WPI-CMC complexes were prepared at 9% protein the acid gels showed improved gel hardness and water holding capacity, which was supported by the more interconnected protein network with less porosity when compared to complexes heated at 6% protein. It is concluded that protein concentration and biopolymer ratio during complex formation are the major factors affecting gel properties while the effect of CMC molecular weight was less significant. © 2016 Institute of Food Technologists®

Exploiting Photo-induced Reactions in Polymer Blends to Create Hierarchically Ordered, Defect-free Materials

ScienceCinema

Balazs, Anna [University of Pittsburgh, Pittsburgh, Pennsylvania, United States

2017-12-09

Computer simulations reveal how photo-induced chemical reactions can be exploited to create long-range order in binary and ternary polymeric materials. The process is initiated by shining a spatially uniform light over a photosensitive AB binary blend, which undergoes both a reversible chemical reaction and phase separation. We then introduce a well-collimated, higher-intensity light source. Rastering this secondary light over the sample locally increases the reaction rate and causes formation of defect-free, spatially periodic structures. These binary structures resemble either the lamellar or hexagonal phases of microphase-separated di-block copolymers. We measure the regularity of the ordered structures as a function of the relative reaction rates for different values of the rastering speed and determine the optimal conditions for creating defect-free structures in the binary systems. We then add a non-reactive homo-polymer C, which is immiscible with both A and B. We show that this component migrates to regions that are illuminated by the secondary, higher-intensity light, allowing us to effectively write a pattern of C onto the AB film. Rastering over the ternary blend with this collimated light now leads to hierarchically ordered patterns of A, B, and C. The findings point to a facile, non-intrusive process for manufacturing high-quality polymeric devices in a low-cost, efficient manner.

Highly Loaded Mesoporous Silica/Nanoparticle Composites and Patterned Mesoporous Silica Films

NASA Astrophysics Data System (ADS)

Kothari, Rohit; Hendricks, Nicholas R.; Wang, Xinyu; Watkins, James J.

2014-03-01

Novel approaches for the preparation of highly filled mesoporous silica/nanoparticle (MS/NP) composites and for the fabrication of patterned MS films are described. The incorporation of iron platinum NPs within the walls of MS is achieved at high NP loadings by doping amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (Pluronic®) copolymer templates via selective hydrogen bonding between the pre-synthesized NPs and the hydrophilic portion of the block copolymer. The MS is then synthesized by means of phase selective condensation of tetraethylorthosilicate (TEOS) within the NP loaded block copolymer templates dilated with supercritical carbon dioxide (scCO2) followed by calcination. For patterned films, microphase separated block copolymer/small molecule additive blends are patterned using UV-assisted nanoimprint lithography. Infusion and condensation of a TEOS within template films using ScCO2 as a processing medium followed by calcination yields the patterned MS films. Scanning electron microscopy is used characterize pattern fidelity and transmission electron microscopy analysis confirms the presence of the mesopores. Long range order in nanocomposites is confirmed by low angle x-ray diffraction.

Diketopyrrolopyrrole Polymers with Thienyl and Thiazolyl Linkers for Application in Field-Effect Transistors and Polymer Solar Cells.

PubMed

Yu, Yaping; Wu, Yang; Zhang, Andong; Li, Cheng; Tang, Zheng; Ma, Wei; Wu, Yonggang; Li, Weiwei

2016-11-09

Conjugated polymers consisting of diketopyrrolopyrrole (DPP) units have been successfully applied in field-effect transistors (FETs) and polymer solar cells (PSCs), while most of the DPP polymers were designed as symmetric structures containing identical aromatic linkers. In this manuscript, we design a new asymmetric DPP polymer with varied aromatic linkers in the backbone for application in FETs and PSCs. The designation provides the chance to finely adjust the energy levels of conjugated polymers so as to influence the device performance. The asymmetric polymer exhibits highly crystalline properties, high hole mobilities of 3.05 cm 2 V -1 s -1 in FETs, and a high efficiency of 5.9% in PSCs with spectra response from 300 to 850 nm. Morphology investigation demonstrates that the asymmetric polymer has a large crystal domain in blended thin films, indicating that the solar cell performance can be further enhanced by optimizing the microphase separation. The study reveals that the asymmetric design via adjusting the aromatic linkers in DPP polymers is a useful route toward flexible electronic devices.

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

PubMed

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.

Dynamic and structural evidence of mesoscopic aggregation in phosphonium ionic liquids

NASA Astrophysics Data System (ADS)

Cosby, T.; Vicars, Z.; Heres, M.; Tsunashima, K.; Sangoro, J.

2018-05-01

Mesoscopic aggregation in aprotic ionic liquids due to the microphase separation of polar and non-polar components is expected to correlate strongly with the physicochemical properties of ionic liquids and therefore their potential applications. The most commonly cited experimental evidence of such aggregation is the observation of a low-q pre-peak in the x-ray and neutron scattering profiles, attributed to the polarity alternation of polar and apolar phases. In this work, a homologous series of phosphonium ionic liquids with the bis(trifluoromethylsulfonyl)imide anion and systematically varying alkyl chain lengths on the phosphonium cation are investigated by small and wide-angle x-ray scattering, dynamic-mechanical spectroscopy, and broadband dielectric spectroscopy. A comparison of the real space correlation distance corresponding to the pre-peak and the presence or absence of the slow sub-α dielectric relaxation previously associated with the motion of mesoscale aggregates reveals a disruption of mesoscale aggregates with increasing symmetry of the quaternary phosphonium cation. These findings contribute to the broader understanding of the interplay of molecular structures, mesoscale aggregation, and physicochemical properties in aprotic ionic liquids.

Rheological Design of Sustainable Block Copolymers

NASA Astrophysics Data System (ADS)

Mannion, Alexander M.

Block copolymers are extremely versatile materials that microphase separate to give rise to a rich array of complex behavior, making them the ideal platform for the development of rheologically sophisticated soft matter. In line with growing environmental concerns of conventional plastics from petroleum feedstocks, this work focuses on the rheological design of sustainable block copolymers--those derived from renewable sources and are degradable--based on poly(lactide). Although commercially viable, poly(lactide) has a number of inherent deficiencies that result in a host of challenges that require both creative and practical solutions that are cost-effective and amenable to large-scale production. Specifically, this dissertation looks at applications in which both shear and extensional rheology dictate performance attributes, namely chewing gum, pressure-sensitive adhesives, and polymers for blown film extrusion. Structure-property relationships in the context of block polymer architecture, polymer composition, morphology, and branching are explored in depth. The basic principles and fundamental findings presented in this thesis are applicable to a broader range of substances that incorporate block copolymers for which rheology plays a pivotal role.

Distinct Tensile Response of Model Semi-flexible Elastomer Networks

NASA Astrophysics Data System (ADS)

Aguilera-Mercado, Bernardo M.; Cohen, Claude; Escobedo, Fernando A.

2011-03-01

Through coarse-grained molecular modeling, we study how the elastic response strongly depends upon nanostructural heterogeneities in model networks made of semi-flexible chains exhibiting both regular and realistic connectivity. Idealized regular polymer networks have been shown to display a peculiar elastic response similar to that of super-tough natural materials (e.g., organic adhesives inside abalone shells). We investigate the impact of chain stiffness, and the effect of including tri-block copolymer chains, on the network's topology and elastic response. We find in some systems a dual tensile response: a liquid-like behavior at small deformations, and a distinct saw-tooth shaped stress-strain curve at moderate to large deformations. Additionally, stiffer regular networks exhibit a marked hysteresis over loading-unloading cycles that can be deleted by heating-cooling cycles or by performing deformations along different axes. Furthermore, small variations of chain stiffness may entirely change the nature of the network's tensile response from an entropic to an enthalpic elastic regime, and micro-phase separation of different blocks within elastomer networks may significantly enhance their mechanical strength. This work was supported by the American Chemical Society.

Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study

NASA Astrophysics Data System (ADS)

Weyman, Alexander; Bier, Markus; Holm, Christian; Smiatek, Jens

2018-05-01

We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids. The ion transport numbers are unaffected by the occurrence of these domains, and the corresponding values highlight the potential role of PILs as single-ion conductors in electrochemical devices. In contrast to bulk behavior, a pronounced formation of ion conductivity channels in confined systems is initiated in close vicinity to the boundaries. We observe higher ion conductivities in these channels for increasing PIL side chain lengths in comparison with bulk values and provide an explanation for this effect. The appearance of these domains points to an improved application of PILs in modern polymer electrolyte batteries.

Intriguing Morphology Evolution from Noncrosslinked Poly(tert-butyl acrylate) Seeds with Polar Functional Groups in Soap-Free Emulsion Polymerization of Styrene.

PubMed

Wang, Lu; Pan, Mingwang; Song, Shaofeng; Zhu, Lei; Yuan, Jinfeng; Liu, Gang

2016-08-09

Herein, we demonstrate a facile approach to prepare anisotropic poly(tert-butyl acrylate)/polystyrene (PtBA/PS) composite particles with controllable morphologies by soap-free seeded emulsion polymerization (SSEP). In the first step, noncrosslinked PtBA seeds with self-stabilizing polar functional groups (e.g., ester groups and radicals) are synthesized by soap-free emulsion polymerization. During the subsequent SSEP of styrene (St), PS bulges are nucleated on the PtBA seeds due to the microphase separation confined in the latex particles. The morphology evolution of PtBA/PS composite particles is tailored by varying the monomer/seed feed ratio, polymerization time, and polymerization temperature. Many intriguing morphologies, including hamburger-like, litchi-like, mushroom-like, strawberry-like, bowl-like, and snowman-like, have been acquired for PtBA/PS composite particles. The polar groups on the PtBA seed surface greatly influence the formation and further merging of PS/St bulges during the polymerization. A possible formation mechanism is proposed on the basis of experimental results. These complex composite particles are promising for applications in superhydrophobic coatings.

Charge segregation in weakly ionized microgels

DOE PAGES

Hyatt, John S.; Douglas, Alison M.; Stanley, Chris; ...

2017-01-19

Here we investigate microgels synthesized from N-isopropylacrylamide (NIPAM) copolymerized with a large mol% of acrylic acid, finding that when the acid groups are partially ionized at high temperatures, competition between ion-induced swelling and hydrophobic deswelling of poly(NIPAM) chains results in microphase separation. In cross-linked microgels, this manifests as a dramatic decrease in the ratio between the radius of gyration and the hydrodynamic radius to ~0.2, indicating that almost all the mass of the microgel is concentrated near the particle center. We also observe a concurrent decrease of the polymer network length scale via small-angle neutron scattering, confirming the presence ofmore » a dense, deswollen core surrounded by a diffuse, charged periphery. We compare these results to those obtained for a system of charged ultralow-cross-linked microgels; the form factor shows a distinct peak at high q when the temperature exceeds a threshold value. Lastly, we successfully fit the form factor to theory developed to describe scattering from weakly charged gels in poor solvents, and we tie this behavior to charge segregation in the case of the cross-linked microgels.« less

Ordered three- and five-ply nanocomposites from ABC block terpolymer microphase separation with niobia and aluminosilicate sols

PubMed Central

Stefik, Morgan; Mahajan, Surbhi; Sai, Hiroaki; Epps, Thomas H.; Bates, Frank S.; Gruner, Sol M; DiSalvo, Francis J.; Wiesner, Ulrich

2009-01-01

We report the first use of a non-frustrated block terpolymer for the synthesis of highly ordered oxide nanocomposites containing multiple plies. The morphological behavior of 15 ISO-oxide nanocomposites was investigated spanning a large range of compositions along the ƒI=ƒS isopleth using aluminosilicate and niobia sols. Morphologies were determined by TEM and SAXS measurements. Four morphologies were identified, including core-shell hexagonal, core-shell double gyroid, three-domain lamellae, and core-shell inverse-hexagonal, in order of increasing O+oxide vol fraction. All of the resulting nanocomposites had three- or five-ply morphologies containing domains that were continuous in one, two, or three dimensions. The five-ply core-shell double gyroid phase was only found to be stable when the O+oxide domain was a minority. Removal of the polymer enabled simple and direct synthesis of mesoporous oxide materials while retaining the ordered network structure. We believe that advances in the synthesis of multi-ply nanocomposites will lead to advanced materials and devices containing multiple plies of functional materials. PMID:20209023

Ordered three- and five-ply nanocomposites from ABC block terpolymer microphase separation with niobia and aluminosilicate sols.

PubMed

Stefik, Morgan; Mahajan, Surbhi; Sai, Hiroaki; Epps, Thomas H; Bates, Frank S; Gruner, Sol M; Disalvo, Francis J; Wiesner, Ulrich

2009-11-24

We report the first use of a non-frustrated block terpolymer for the synthesis of highly ordered oxide nanocomposites containing multiple plies. The morphological behavior of 15 ISO-oxide nanocomposites was investigated spanning a large range of compositions along the ƒ(I)=ƒ(S) isopleth using aluminosilicate and niobia sols. Morphologies were determined by TEM and SAXS measurements. Four morphologies were identified, including core-shell hexagonal, core-shell double gyroid, three-domain lamellae, and core-shell inverse-hexagonal, in order of increasing O+oxide vol fraction. All of the resulting nanocomposites had three- or five-ply morphologies containing domains that were continuous in one, two, or three dimensions. The five-ply core-shell double gyroid phase was only found to be stable when the O+oxide domain was a minority. Removal of the polymer enabled simple and direct synthesis of mesoporous oxide materials while retaining the ordered network structure. We believe that advances in the synthesis of multi-ply nanocomposites will lead to advanced materials and devices containing multiple plies of functional materials.

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

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

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

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

Dynamic photoinduced realignment processes in photoresponsive block copolymer films: effects of the chain length and block copolymer architecture.

PubMed

Sano, Masami; Shan, Feng; Hara, Mitsuo; Nagano, Shusaku; Shinohara, Yuya; Amemiya, Yoshiyuki; Seki, Takahiro

2015-08-07

A series of block copolymers composed of an amorphous poly(butyl methacrylate) (PBMA) block connected with an azobenzene (Az)-containing liquid crystalline (PAz) block were synthesized by changing the chain length and polymer architecture. With these block copolymer films, the dynamic realignment process of microphase separated (MPS) cylinder arrays of PBMA in the PAz matrix induced by irradiation with linearly polarized light was studied by UV-visible absorption spectroscopy, and time-resolved grazing incidence small angle X-ray scattering (GI-SAXS) measurements using a synchrotron beam. Unexpectedly, the change in the chain length hardly affected the realignment rate. In contrast, the architecture of the AB-type diblock or the ABA-type triblock essentially altered the realignment feature. The strongly cooperative motion with an induction period before realignment was characteristic only for the diblock copolymer series, and the LPL-induced alignment change immediately started for triblock copolymers and the PAz homopolymer. Additionally, a marked acceleration in the photoinduced dynamic motions was unveiled in comparison with a thermal randomization process.

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

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

Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi

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 thismore » 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 “dead ends” in the conducting channel due to poor continuity across grain boundaries in the ordered state and the formation of concave interfaces in the disordered state. The results demonstrate that disordered, microphase-separated morphologies provide better transport properties than compositionally equivalent polycrystalline systems with long-range order, an important criterion when optimizing the design of polymer electrolytes.« less

Self-oscillating AB diblock copolymer developed by post modification strategy

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

Ueki, Takeshi, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp; Onoda, Michika; Tamate, Ryota

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 atmore » 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.« less

Measurements in a Transitional Boundary Layer Under Low-Pressure Turbine Airfoil Conditions

NASA Technical Reports Server (NTRS)

Simon, Terrence W.; Qiu, Songgang; Yuan, Kebiao; Ashpis, David (Technical Monitor); Simon, Fred (Technical Monitor)

2000-01-01

This report presents the results of an experimental study of transition from laminar to turbulent flow in boundary layers or in shear layers over separation zones on a convex-curved surface which simulates the suction surface of a low-pressure turbine airfoil. Flows with various free-stream turbulence intensity (FSTI) values (0.5%, 2.5% and 10%), and various Reynolds numbers (50,000, 100,000 200,000 and 300,000) are investigated. Reynold numbers in the present study are based on suction surface length and passage exit mean velocity. Flow separation followed by transition within the separated flow region is observed for the lower-Re cases at each of the FSTI levels. At the highest Reynolds numbers and at elevated FSn, transition of the attached boundary layer begins before separation, and the separation zone is small. Transition proceeds in the shear layer over the separation bubble. For both the transitional boundary layer and the transitional shear layer, mean velocity, turbulence intensity and intermittency (the fraction of the time the flow is turbulent) distributions are presented. The present data are compared to published distribution models for bypass transition, intermittency distribution through transition, transition start position, and transition length. A model developed for transition of separated flows is shown to adequately predict the location of the beginning of transition, for these cases, and a model developed for transitional boundary layer flows seems to adequately predict the path of intermittency through transition when the transition start and end are known. These results are useful for the design of low-pressure turbine stages which are known to operate under conditions replicated by these tests.

"Student Lab"-on-a-Chip: Integrating Low-Cost Microfluidics into Undergraduate Teaching Labs to Study Multiphase Flow Phenomena in Small Vessels

ERIC Educational Resources Information Center

Young, Edmond W. K.; Simmons, Craig A.

2009-01-01

We describe a simple, low-cost laboratory session to demonstrate the Fahraeus-Lindqvist effect, a microphase flow phenomenon that occurs in small blood vessels and alters the effective rheological properties of blood. The experiments are performed by flowing cells through microchannels fabricated by soft lithography and characterization of cell…

Solid-Liquid Electrolyte as a Nanoion Modulator for Dendrite-Free Lithium Anodes.

PubMed

Wen, Kaihua; Wang, Yanlei; Chen, Shimou; Wang, Xi; Zhang, Suojiang; Archer, Lynden A

2018-06-20

Rechargeable lithium (Li) metal batteries are considered the most promising of Li-based energy storage technologies. However, tree-like dendrite produced by irregular Li + electrodeposition restricts it wide applications. Herein, based on a cation-microphase-regulation strategy, we create solid-liquid electrolytes (SLEs) by absorbing commercial liquid electrolytes into polyethylene glycol (PEG) engineered nanoporous Al 2 O 3 ceramic membranes. By means of molecular dynamics simulations and comprehensive experiments, we show that Li ions are regulated and promoted in the two microphases, the channel phase and nonchannel phase, respectively. The channel phase can achieve homogeneous Li + flux distribution by multiple mechanisms, including its uniform array of nanochannels and ability to suppress lateral dendrite growth by its high modulus. In the nonchannel phase, PEG chains swollen by electrolyte facilitate desolvation and fast conduction of Li + . As a result, the studied SLEs exhibit high ionic conductivity, low interfacial resistance, and the unique ability to stabilize deposition at the Li anode. By means of galvanostatic cycling studies in symmetric Li cells and Li/Li 4 Ti 5 O 12 cells, we further show that the materials open a path to Li metal batteries with excellent cycling performance.

The geochemical and genetic role of organic substances in postmagmatic derivatives of alkaline plutons

NASA Astrophysics Data System (ADS)

Ermolaeva, V. N.; Chukanov, N. V.; Pekov, I. V.; Kogarko, L. N.

2009-12-01

Solid bituminous substances (SBS) are common components of the late hydrothermal mineral assemblages of peralkaline pegmatites. SBS are formed in a reductive setting as a result of progressive sorption of minor carbon-bearing molecules (CO, CO2, CH4, C2H6, C2H4, etc.), their polymerization, transformation into aromatic compounds (reformation), and selective oxidation on microporous zeolite-like Ti-, Nb-, and Zrsilicates serving as sorbents and catalysts. The oxygen-bearing aromatic compounds with hydrophile functional groups (-OH, -C=O, -COOH, -COO) act as complexing agents with respect to Th, REE, U, Zr, Ti, Nb, Ba, Sr, Ca, resulting in transfer of these bitumenophile elements under low-temperature hydrothermal conditions in the form of water-soluble macroassociates of the micelle type. Th, REE, and to a lesser extent, U, Zr, Ti, and Nb concentrate at the late stage of the hydrothermal process as microphases impregnating SBS or macroscopic segregations of Th and REE minerals. At the final stage, homogeneous SBS break down into organic (partly together with Ca, Sr, Ba, and Pb) and mineral (with Th, Ln, Y, Ti, Nb, Ca, Na, K, Si) microphases.

Coupling mesodomain positional ordering to intra-domain orientational ordering in block copolymer assembly

NASA Astrophysics Data System (ADS)

Burke, Christopher; Reddy, Abhiram; Prasad, Ishan; Grason, Gregory

Block copolymer (BCP) melts form a number of symmetric microphases, e.g. columnar or double gyroid phases. BCPs with a block composed of chiral monomers are observed to form bulk phases with broken chiral symmetry e.g. a phase of hexagonally ordered helical mesodomains. Other new structures may be possible, e.g. double gyroid with preferred chirality which has potential photonic applications. One approach to understanding chirality transfer from monomer to the bulk is to use self consistent field theory (SCFT) and incorporate an orientational order parameter with a preference for handed twist in chiral block segments, much like the texture of cholesteric liquid crystal. Polymer chains in achiral BCPs exhibit orientational ordering which couples to the microphase geometry; a spontaneous preference for ordering may have an effect on the geometry. The influence of a preference for chiral polar (vectorial) segment order has been studied to some extent, though the influence of coupling to chiral tensorial (nematic) order has not yet been developed. We present a computational approach using SCFT with vector and tensor order which employs well developed pseudo-spectral methods. Using this we explore how tensor order influences which structures form, and if it can promote chiral phases.

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

PubMed

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

2007-04-12

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

Analysis of airfoil transitional separation bubbles

NASA Technical Reports Server (NTRS)

Davis, R. L.; Carter, J. E.

1984-01-01

A previously developed local inviscid-viscous interaction technique for the analysis of airfoil transitional separation bubbles, ALESEP (Airfoil Leading Edge Separation) has been modified to utilize a more accurate windward finite difference procedure in the reversed flow region, and a natural transition/turbulence model has been incorporated for the prediction of transition within the separation bubble. Numerous calculations and experimental comparisons are presented to demonstrate the effects of the windward differencing scheme and the natural transition/turbulence model. Grid sensitivity and convergence capabilities of this inviscid-viscous interaction technique are briefly addressed. A major contribution of this report is that with the use of windward differencing, a second, counter-rotating eddy has been found to exist in the wall layer of the primary separation bubble.

Metal Ion-Loaded Nanofibre Matrices for Calcification Inhibition in Polyurethane Implants

PubMed Central

Singh, Charanpreet; Wang, Xungai

2017-01-01

Pathologic calcification leads to structural deterioration of implant materials via stiffening, stress cracking, and other structural disintegration mechanisms, and the effect can be critical for implants intended for long-term or permanent implantation. This study demonstrates the potential of using specific metal ions (MI)s for inhibiting pathological calcification in polyurethane (PU) implants. The hypothesis of using MIs as anti-calcification agents was based on the natural calcium-antagonist role of Mg2+ ions in human body, and the anti-calcification effect of Fe3+ ions in bio-prosthetic heart valves has previously been confirmed. In vitro calcification results indicated that a protective covering mesh of MI-doped PU can prevent calcification by preventing hydroxyapatite crystal growth. However, microstructure and mechanical characterisation revealed oxidative degradation effects from Fe3+ ions on the mechanical properties of the PU matrix. Therefore, from both a mechanical and anti-calcification effects point of view, Mg2+ ions are more promising candidates than Fe3+ ions. The in vitro MI release experiments demonstrated that PU microphase separation and the structural design of PU-MI matrices were important determinants of release kinetics. Increased phase separation in doped PU assisted in consistent long-term release of dissolved MIs from both hard and soft segments of the PU. The use of a composite-sandwich mesh design prevented an initial burst release which improved the late (>20 days) release rate of MIs from the matrix. PMID:28644382

Polymer compositions based on PXE

DOEpatents

Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

2015-09-15

New polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers.

Shape Recovery with Concomitant Mechanical Strengthening of Amphiphilic Shape Memory Polymers in Warm Water

DOE PAGES

Zhang, Ben; DeBartolo, Janae E.; Song, Jie

2017-01-26

Maintaining adequate or enhancing mechanical properties of shape memory polymers (SMPs) after shape recovery in an aqueous environment are greatly desired for biomedical applications of SMPs as self-fitting tissue scaffolds or minimally invasive surgical implants. Here we report stable temporary shape fixing and facile shape recovery of biodegradable triblock amphiphilic SMPs containing a poly(ethylene glycol) (PEG) center block and flanking poly(lactic acid) or poly(lactic-co-glycolic acid) blocks in warm water, accompanied with concomitant enhanced mechanical strengths. Differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WXRD) and small-angle X-ray scattering (SAXS) analyses revealed that the unique stiffening of the amphiphilic SMPs upon hydrationmore » was due to hydration-driven microphase separation and PEG crystallization. We further demonstrated that the chemical composition of degradable blocks in these SMPs could be tailored to affect the persistence of hydration-induced stiffening upon subsequent dehydration. These properties combined open new horizons for these amphiphilic SMPs for smart weight-bearing in vivo applications (e.g. as self-fitting intervertebral discs). In conclusion, this study also provides a new material design strategy to strengthen polymers in aqueous environment in general.« less

Development of Ordered, Porous (Sub-25 nm Dimensions) Surface Membrane Structures Using a Block Copolymer Approach.

PubMed

Ghoshal, Tandra; Holmes, Justin D; Morris, Michael A

2018-05-08

In an effort to develop block copolymer lithography to create high aspect vertical pore arrangements in a substrate surface we have used a microphase separated poly(ethylene oxide) -b- polystyrene (PEO-b-PS) block copolymer (BCP) thin film where (and most unusually) PS not PEO is the cylinder forming phase and PEO is the majority block. Compared to previous work, we can amplify etch contrast by inclusion of hard mask material into the matrix block allowing the cylinder polymer to be removed and the exposed substrate subject to deep etching thereby generating uniform, arranged, sub-25 nm cylindrical nanopore arrays. Briefly, selective metal ion inclusion into the PEO matrix and subsequent processing (etch/modification) was applied for creating iron oxide nanohole arrays. The oxide nanoholes (22 nm diameter) were cylindrical, uniform diameter and mimics the original BCP nanopatterns. The oxide nanohole network is demonstrated as a resistant mask to fabricate ultra dense, well ordered, good sidewall profile silicon nanopore arrays on substrate surface through the pattern transfer approach. The Si nanopores have uniform diameter and smooth sidewalls throughout their depth. The depth of the porous structure can be controlled via the etch process.

Structure-properties relationships of novel poly(carbonate-co-amide) segmented copolymers with polyamide-6 as hard segments and polycarbonate as soft segments

NASA Astrophysics Data System (ADS)

Yang, Yunyun; Kong, Weibo; Yuan, Ye; Zhou, Changlin; Cai, Xufu

2018-04-01

Novel poly(carbonate-co-amide) (PCA) block copolymers are prepared with polycarbonate diol (PCD) as soft segments, polyamide-6 (PA6) as hard segments and 4,4'-diphenylmethane diisocyanate (MDI) as coupling agent through reactive processing. The reactive processing strategy is eco-friendly and resolve the incompatibility between polyamide segments and PCD segments in preparation processing. The chemical structure, crystalline properties, thermal properties, mechanical properties and water resistance were extensively studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Differential scanning calorimetry (DSC), Thermal gravity analysis (TGA), Dynamic mechanical analysis (DMA), tensile testing, water contact angle and water absorption, respectively. The as-prepared PCAs exhibit obvious microphase separation between the crystalline hard PA6 phase and amorphous PCD soft segments. Meanwhile, PCAs showed outstanding mechanical with the maximum tensile strength of 46.3 MPa and elongation at break of 909%. The contact angle and water absorption results indicate that PCAs demonstrate outstanding water resistance even though possess the hydrophilic surfaces. The TGA measurements prove that the thermal stability of PCA can satisfy the requirement of multiple-processing without decomposition.

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

Wang, Wenwen; Wang, Weiyu; Li, Hui

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Fluids density functional theory and initializing molecular dynamics simulations of block copolymers

NASA Astrophysics Data System (ADS)

Brown, Jonathan R.; Seo, Youngmi; Maula, Tiara Ann D.; Hall, Lisa M.

2016-03-01

Classical, fluids density functional theory (fDFT), which can predict the equilibrium density profiles of polymeric systems, and coarse-grained molecular dynamics (MD) simulations, which are often used to show both structure and dynamics of soft materials, can be implemented using very similar bead-based polymer models. We aim to use fDFT and MD in tandem to examine the same system from these two points of view and take advantage of the different features of each methodology. Additionally, the density profiles resulting from fDFT calculations can be used to initialize the MD simulations in a close to equilibrated structure, speeding up the simulations. Here, we show how this method can be applied to study microphase separated states of both typical diblock and tapered diblock copolymers in which there is a region with a gradient in composition placed between the pure blocks. Both methods, applied at constant pressure, predict a decrease in total density as segregation strength or the length of the tapered region is increased. The predictions for the density profiles from fDFT and MD are similar across materials with a wide range of interfacial widths.

Substrate effect on nanoporous structure of silica wires by channel-confined self-assembly of block-copolymer and sol-gel precursors

DOE PAGES

Hu, Michael Z.; Lai, Peng

2015-09-22

Nanoporous silica wires of various wire diameters were developed by space-confined molecular self-assembly of triblock copolymer ethylene/propylene/ethylene (P123) and silica alkoxide precursor (tetraethylorthosilicate, TEOS). Two distinctive hard-templating substrates, anodized aluminum oxide (AAO) and track-etched polycarbonate (EPC), with channel diameters in the range between 10 nm and 200 nm were employed for space-confinement of soft molecular self-assembly driven by the block-copolymer microphase separation. It was observed in the scanning and transmission electron microscope (STEM) studies that the substrate geometry and material characteristics had pronounced effects on the structure and morphology of the silica nanowires. A substrate wall effect was proposed tomore » explain the ordering and orientation of the intra-wire mesostructure. Circular and spiral nanostructures were found only in wires formed in AAO substrate, not in EPC. Pore-size differences and distinctive wall morphologies of the nanowires relating to the substrates were discussed. It was shown that the material and channel wall characteristics of different substrates play key roles in the ordering and morphology of the intra-wire nanostructures.« less

Molecular-level Simulations of Shock Generation and Propagation in Polyurea

DTIC Science & Technology

2011-01-26

homepage: www.e lsev ier .com/ locate /msea Molecular-level simulations of shock generation and propagation in polyurea M. Grujicica,∗, B. Pandurangana... Polyurea Shock-wave generation and propagation Molecular-level calculations a b s t r a c t A non-equilibrium molecular dynamics method is employed in order...to study various phenomena accompanying the generation and propagation of shock waves in polyurea (a micro-phase segregated elastomer). Several

Macroscopic Modeling of A3B15A3 Triblock Copolymers in B Solvent

DTIC Science & Technology

2010-11-01

matrix composed of the midblock (2). Some examples of TPEs are poly[styrene-butadiene-styrene] (SBS), poly[styrene- isoprene -styrene] (SIS), poly[styrene...92. 19. Hadziioannou, G.; Skoulios, A. Molecular Weight Dependence of Lamellar Structure in Styrene Isoprene Two- and Three-block Copolymers...Microphase Seperation in Styrene- Isoprene Block Copolymers. Macromolecules 1994, 27. 42. Mckay, K. W.; Gros, W. A.; Diehl, C. F. The Influence of

Experimental Study of Transitional Flow Behavior in a Simulated Low Pressure Turbine

NASA Technical Reports Server (NTRS)

Sohn, Ki Hyeon; DeWitt, Kenneth J.

1998-01-01

A detailed investigation of the flow physics occurring on the suction side of a simulated Low Pressure Turbine (LPT) blade was performed. A contoured upper wall was designed to simulate the pressure distribution of an actual LPT airfoil onto a flat lower plate. The experiments were carried out for the Reynolds numbers of 35,000, 70,000, 100,000 and 250,000 with four levels of freestream turbulence ranging from 1% to 4%. For the three lower Reynolds numbers, the boundary layer on the flat plate was separated and formed a bubble. The size of laminar separation bubble was measured to be inversely proportional to the freestream turbulence levels and Reynolds numbers. However, no separation was observed for the Re = 250,000 case. The transition on a separated flow was found to proceed through the formation of turbulent spots in the free shear layer as evidenced in the intermittency profiles for Re = 35,000, 70,000 and 100,000. Spectral data show no evidence of Kelvin-Helmholtz or Tollmien-Schlichting instability waves in the free shear layer over a separation bubble (bypass transition). However, the flow visualization revealed the large vortex structures just outside of the bubble and their development to turbulent flow for Re = 50,000, which is similar to that in the free shear layer (separated-flow transition). Therefore, it is fair to say that the bypass and separated-flow transition modes coexist in the transitional flows over the separation bubble for certain conditions. Transition onset and end locations and length determined from intermittency profiles decrease as Reynolds number and freestream turbulence levels increase.

Experimental Study of Transitional Flow Behavior in a Simulated Low Pressure Turbine

NASA Technical Reports Server (NTRS)

Sohn, Ki Hyeon; DeWitt, Kenneth J.

2007-01-01

A detailed investigation of the flow physics occurring on the suction side of a simulated Low Pressure Turbine (LPT) blade was performed. A contoured upper wall was designed to simulate the pressure distribution of an actual LPT airfoil onto a flat lower plate. The experiments were carried out for the Reynolds numbers of 35,000, 70,000, 100,000, and 250,000 with four levels of freestream turbulence ranging from 1 to 4 percent. For the three lower Reynolds numbers, the boundary layer on the flat plate was separated and formed a bubble. The size of laminar separation bubble was measured to be inversely proportional to the freestream turbulence levels and Reynolds numbers. However, no separation was observed for the Re = 250,000 case. The transition on a separated flow was found to proceed through the formation of turbulent spots in the free shear layer as evidenced in the intermittency profiles for Re = 35,000, 70,000, and 100,000. Spectral data show no evidence of Kelvin-Helmholtz of Tollmien-Schlichting instability waves in the free shear layer over a separation bubble (bypass transition). However, the flow visualization revealed the large vortex structures just outside of the bubble and their development to turbulent flow for Re = 50,000, which is similar to that in the free shear layer (separated-flow transition). Therefore, it is fair to say that the bypass and separated-flow transition modes coexist in the transition flows over the separation bubble of certain conditions. Transition onset and end locations and length determined from intermittency profiles decreased as Reynolds number and freestream turbulence levels increase.

Flight-measured laminar boundary-layer transition phenomena including stability theory analysis

NASA Technical Reports Server (NTRS)

Obara, C. J.; Holmes, B. J.

1985-01-01

Flight experiments were conducted on a single-engine turboprop aircraft fitted with a 92-in-chord, 3-ft-span natural laminar flow glove at glove section lift coefficients from 0.15 to 1.10. The boundary-layer transition measurement methods used included sublimating chemicals and surface hot-film sensors. Transition occurred downstream of the minimum pressure point. Hot-film sensors provided a well-defined indication of laminar, laminar-separation, transitional, and turbulent boundary layers. Theoretical calculations of the boundary-layer parameters provided close agreement between the predicted laminar-separation point and the measured transition location. Tollmien-Schlichting (T-S) wave growth n-factors between 15 and 17 were calculated at the predicted point of laminar separation. These results suggest that for many practical airplane cruise conditions, laminar separation (as opposed to T-S instability) is the major cause of transition in predominantly two-dimensional flows.

Synthesis of a novel biomedical poly(ester urethane) based on aliphatic uniform-size diisocyanate and the blood compatibility of PEG-grafted surfaces.

PubMed

Liu, Xiaolong; Xia, Yiran; Liu, Lulu; Zhang, Dongmei; Hou, Zhaosheng

2018-05-01

The purpose of this study is to offer a novel kind of polyurethane with improved surface blood compatibility for long-term implant biomaterials. In this work, the aliphatic poly(ester-urethane) (PEU) with uniform-size hard segments was prepared and the PEU surface was grafted with hydrophilic poly(ethylene glycol) (PEG). The PEU was obtained by chain-extension of poly(ɛ-caprolactone) (PCL) with isocyanate-terminated urethane triblock. Free amino groups were introduced onto the surface of PEU film via aminolysis with hexamethylenediamine, and then the NH 2 -grafted PEU surfaces (PEU-NH 2 ) were reacted with isocyanate-terminated monomethoxyl PEG (MPEG-NCO) to obtain the PEG-grafted PEU surfaces (PEU-PEG). Analysis by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and gel permeation chromatography were performed to confirm the chemical structures of the chain extender, PCL, PEU, and PEU-PEG. Additionally, the influence of aminolysis on the physical-mechanical properties of PEU films was investigated. Two glass transition temperatures and a broad endothermic peak were observed in the differential scanning calorimetry curves of PEU, which demonstrated a microphase-separated and semicrystalline structure, respectively. The PEU-PEG film exhibited excellent mechanical properties with an ultimate stress of ∼39 MPa and an elongation at break of ∼1190%, which was slightly lower than that of PEU, indicating that the aminolysis has little influence on the tensile properties. Evaluation of the blood compatibility of the films by bovine serum albumin adsorption and the platelet adhesion test revealed that the PEG-grafted surface had improved resistance to protein adsorption and excellent resistance to platelet adhesion. In vitro degradation tests showed that the PEU-PEG film could maintain its mechanical properties for more than six months and only lost ∼25% weight after 18 months. Due to the excellent mechanical properties, good blood compatibility and slow degradability, this novel kind of polyurethane hold significant promise for long-term implant biomaterials, especially soft tissue augmentation and regeneration.

Self assembly and shear induced morphologies of asymmetric block copolymers with spherical domains

NASA Astrophysics Data System (ADS)

Mandare, Prashant N.

2007-12-01

Microphase separated block copolymers have been subject of investigation for past two decades. While most of the work is focused on classical phases of lamellae or cylinders, spherical phases have received less attention. The present study deals with the self-assembly in spherical phases of block copolymers that results into formation of a three-dimensional cubic lattice. A model triblock copolymer with several transition temperatures is chosen. Solidification in this model system results from either the arrangement of nanospheres of minor block on a BCC lattice or by formation of physical network where the nanospheres act as crosslinks. The solid-like behavior is characterized by extremely slow relaxation modes. Long time stress relaxation of the model material was examined to distinguish between the solid and liquid behavior. Stress relaxation data from a conventional rheometer was extended to very long times by using a newly built instrument, Relaxometer. The BCC lattice structure of the material behaves as liquid over long time except at low temperatures where an equilibrium modulus is observed. This long time behavior was extended to low shear rate behavior using steady shear rheology. The zero shear viscosity observed at extremely low shear rates has a very high value that is close to the viscosity calculated from stress relaxation experiments. The steady shear viscosity decreases by several orders of magnitude over a small range of shear rates. SAXS experiments on samples sheared even at very low rates indicated loss of the BCC order that was present in the annealed samples before shearing. In the second part, response of the BCC microstructure to large stress was explored. Shearing at constant rate and with LAOS at low frequencies lead to destruction of BCC lattice. The structure recovers upon cessation of the shear with kinetics similar to the one following thermal quench. Under certain conditions, LAOS leads to formation of monodomain textures. At low frequencies, there exists an upper and lower bound on strain amplitude where mono-domain textures can be obtained. Upon alignment, the modulus drops by about 30%. Measurement of rheological properties offers an indirect method to distinguish between polycrystalline structure and monodomain texture.

Interactions between coherent twin boundaries and phase transition of iron under dynamic loading and unloading

NASA Astrophysics Data System (ADS)

Wang, Kun; Chen, Jun; Zhang, Xueyang; Zhu, Wenjun

2017-09-01

Phase transitions and deformation twins are constantly reported in many BCC metals under high pressure, whose interactions are of fundamental importance to understand the strengthening mechanism of these metals under extreme conditions. However, the interactions between twins and phase transition in BCC metals remain largely unexplored. In this work, interactions between coherent twin boundaries and α ↔ ɛ phase transition of iron are investigated using both non-equilibrium molecular dynamics simulations and the nudged elastic band method. Mechanisms of both twin-assisted phase transition and reverse phase transition are studied, and orientation relationships between BCC and HCP phases are found to be ⟨"separators="|11 1 ¯ ⟩ B C C||⟨"separators="|1 ¯2 1 ¯ 0 ⟩ H C P and ⟨"separators="|1 1 ¯ 0 ⟩ B C C||⟨"separators="|0001 ⟩ H C P for both cases. The twin boundary corresponds to {"separators="|10 1 ¯ 0 } H C P after the phase transition. It is amazing that the reverse transition seems to be able to "memorize" and recover the initial BCC twins. The memory would be partly lost when plastic slips take place in the HCP phase before the reverse transition. In the recovered initial BCC twins, three major twin spacings are observed, which are well explained in terms of energy barriers of transition from the HCP phase to the BCC twin. Besides, the variant selection rule of the twin assisted phase transition is also discussed. The results of present work could be expected to give some clues for producing ultra-fine grain structures in materials exhibiting martensitic phase transition.

Self-Assembling Block Copolymer Resist Mixtures towards Lithographic Resists for Sub-10 nm Features

NASA Astrophysics Data System (ADS)

Chandler, Curran; Daga, Vikram; Watkins, James

2009-03-01

Significant improvements in 193 nm photolithography have enabled the extension of device feature sizes beyond the 45 nm and 32 nm nodes, yet uncertainty lies beyond 22 nm features as no single replacement has emerged. Here we show that low molecular weight, nonionic block copolymer surfactant blends are capable of self-assembling into highly ordered domains with feature sizes on the order of 5 nm. These surfactants, most of which lack the required χN for microphase separation on their own, exhibit strong segregation and long-range order upon addition of a component capable of multi-point hydrogen bonding that is specific for one of the blocks in the copolymer. This has been demonstrated by our SAXS data for several Pluronic (PEO-b-PPO-b-PEO) and Brij (PEO-b-[CH2]nCH3) surfactants of various molecular weights and PEO volume fractions. Furthermore, we employ these highly-ordered systems as thin film, nanolithographic etch masks for the transfer of sub-10 nm patterns into silicon-based substrates. Small molecule, hydrogen bonding additives containing aromatic or silsesquioxane structure are also used to tune etch contrast between the blocks which is important for reducing line edge roughness (LER) of such small features.

Coarse-Grained Molecular Monte Carlo Simulations of Liquid Crystal-Nanoparticle Mixtures

NASA Astrophysics Data System (ADS)

Neufeld, Ryan; Kimaev, Grigoriy; Fu, Fred; Abukhdeir, Nasser M.

Coarse-grained intermolecular potentials have proven capable of capturing essential details of interactions between complex molecules, while substantially reducing the number of degrees of freedom of the system under study. In the domain of liquid crystals, the Gay-Berne (GB) potential has been successfully used to model the behavior of rod-like and disk-like mesogens. However, only ellipsoid-like interaction potentials can be described with GB, making it a poor fit for many real-world mesogens. In this work, the results of Monte Carlo simulations of liquid crystal domains using the Zewdie-Corner (ZC) potential are presented. The ZC potential is constructed from an orthogonal series of basis functions, allowing for potentials of essentially arbitrary shapes to be modeled. We also present simulations of mixtures of liquid crystalline mesogens with nanoparticles. Experimentally these mixtures have been observed to exhibit microphase separation and formation of long-range networks under some conditions. This highlights the need for a coarse-grained approach which can capture salient details on the molecular scale while simulating sufficiently large domains to observe these phenomena. We compare the phase behavior of our simulations with that of a recently presented continuum theory. This work was made possible by the Natural Sciences and Engineering Research Council of Canada and Compute Ontario.

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing.

PubMed

Zhou, Zhengping; Liu, Guoliang

2017-04-01

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal-free polyacrylonitrile-containing block copolymers is described. A high-molecular-weight poly(acrylonitrile-block-methyl methacrylate) (PAN-b-PMMA) is synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self-assembly behavior of PAN-b-PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as-spin-coated PAN-b-PMMA is microphase-separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN-b-PMMA into mesoporous carbon thin films, the pore size and center-to-center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conjugated block copolymers as model materials to examine charge transfer in donor-acceptor systems

NASA Astrophysics Data System (ADS)

Gomez, Enrique; Aplan, Melissa; Lee, Youngmin

Weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. The lack of control of interfacial structure has also prevented studies of how driving forces promote charge photogeneration, leading to conflicting hypotheses in the organic photovoltaic literature. Our approach has focused on utilizing block copolymer architectures -where critical interfaces are controlled and stabilized by covalent bonds- to provide the hierarchical structure needed for high-performance organic electronics from self-assembled soft materials. For example, we have demonstrated control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers to achieve 3% power conversion efficiencies in non-fullerene photovoltaics. Furthermore, incorporating the donor-acceptor interface within the molecular structure facilitates studies of charge transfer processes. Conjugated block copolymers enable studies of the driving force needed for exciton dissociation to charge transfer states, which must be large to maximize charge photogeneration but must be minimized to prevent losses in photovoltage in solar cell devices. Our work has systematically varied the chemical structure, energetics, and dielectric constant to perturb charge transfer. As a consequence, we predict a minimum dielectric constant needed to minimize the driving force and therefore simultaneously maximize photocurrent and photovoltage in organic photovoltaic devices.

Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Li, Hui; ...

2015-01-14

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Derivation of Multiple Covarying Material and Process Parameters Using Physics-Based Modeling of X-ray Data

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

Khaira, Gurdaman; Doxastakis, Manolis; Bowen, Alec

There is considerable interest in developing multimodal characterization frameworks capable of probing critical properties of complex materials by relying on distinct, complementary methods or tools. Any such framework should maximize the amount of information that is extracted from any given experiment and should be sufficiently powerful and efficient to enable on-the-fly analysis of multiple measurements in a self-consistent manner. Such a framework is demonstrated in this work in the context of self-assembling polymeric materials, where theory and simulations provide the language to seamlessly mesh experimental data from two different scattering measurements. Specifically, the samples considered here consist of diblock copolymersmore » (BCP) that are self-assembled on chemically nanopatterned surfaces. The copolymers microphase separate into ordered lamellae with characteristic dimensions on the scale of tens of nanometers that are perfectly aligned by the substrate over macroscopic areas. These aligned lamellar samples provide ideal standards with which to develop the formalism introduced in this work and, more generally, the concept of high-information-content, multimodal experimentation. The outcomes of the proposed analysis are then compared to images generated by 3D scanning electron microscopy tomography, serving to validate the merit of the framework and ideas proposed here.« less

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

Experimental Investigation of Separated and Transitional Boundary Layers Under Low-Pressure Turbine Airfoil Conditions

NASA Technical Reports Server (NTRS)

Hultgren, Lennart S.; Volino, Ralph J.

2002-01-01

Modern low-pressure turbine airfoils are subject to increasingly stronger pressure gradients as designers impose higher loading in an effort to improve efficiency and to reduce part count. The adverse pressure gradients on the suction side of these airfoils can lead to boundary-layer separation, particularly under cruise conditions. Separation bubbles, notably those which fail to reattach, can result in a significant degradation of engine efficiency. Accurate prediction of separation and reattachment is hence crucial to improved turbine design. This requires an improved understanding of the transition flow physics. Transition may begin before or after separation, depending on the Reynolds number and other flow conditions, has a strong influence on subsequent reattachment, and may even eliminate separation. Further complicating the problem are the high free-stream turbulence levels in a real engine environment, the strong pressure gradients along the airfoils, the curvature of the airfoils, and the unsteadiness associated with wake passing from upstream stages. Because of the complicated flow situation, transition in these devices can take many paths that can coexist, vary in importance, and possibly also interact, at different locations and instances in time. The present work was carried out in an attempt to systematically sort out some of these issues. Detailed velocity measurements were made along a flat plate subject to the same nominal dimensionless pressure gradient as the suction side of a modern low-pressure turbine airfoil ('Pak-B'). The Reynolds number based on wetted plate length and nominal exit velocity, Re, was varied from 50;000 to 300; 000, covering cruise to takeoff conditions. Low, 0.2%, and high, 7%, inlet free-stream turbulence intensities were set using passive grids. These turbulence levels correspond to about 0.2% and 2.5% turbulence intensity in the test section when normalized with the exit velocity. The Reynolds number and free-stream turbulence level do not have a significant effect on the location of boundary-layer separation unless they are high enough to induce transition upstream of separation. The location and extent of the transition zone, in contrast, depend strongly on Re and TI. The beginning of reattachment closely follows the onset of transition. Under low free-stream turbulence conditions the boundary layer is laminar at separation and then begins to exhibit fluctuations in a finite frequency band in the shear layer over the separation bubble. These fluctuations are due to instability waves. The fluctuations grow in magnitude, higher harmonics are generated, and finally lead to a breakdown to turbulence. Transition begins in the shear layer, but quickly spreads to the near wall region and causes the boundary layer to reattach. The transition is rapid and the resulting turbulence contains a full range of high and low frequencies. Under high free-stream turbulence conditions, slowly growing low-frequency fluctuations are induced in the pretransitional boundary layer by the free-stream. The separation bubbles are considerably thinner than in the low TI cases, resulting in thinner boundary layers at the end of the test wall. At Re=50,000 and 100,000, the pre-transitional boundary layer separates at about the same location as in the low TI cases. Transition occurs through a bypass mode, begins upstream of the corresponding low-TI location, and proceeds in a manner similar to that of an attached boundary layer. Under high TI at Re=200,000 and 300,000, transition begins before separation. The boundary layer may separate, but if it does the separation bubble is very short and does not significantly affect the downstream development of the boundary layer. A comparison is made to previous work in a simulated cascade.

Thermomechanical analysis and durability of commercial micro-porous polymer Li-ion battery separators

NASA Astrophysics Data System (ADS)

Love, Corey T.

2011-03-01

Static and dynamic thermomechanical analysis was performed with a dynamic mechanical analyzer (DMA) to identify thermal and mechanical transitions for commercially available polymer separators under mechanical loading. Clear transitions in deformation mode were observed at elevated temperatures. These transitions identified the onset of separator "shutdown" which occurred at temperatures below the polymer melting point. Mechanical loading direction was critical to the overall integrity of the separator. Anisotropic separators (Celgard 2320, 2400 and 2500) were mechanically limited when pulled in tensile in the transverse direction. The anisotropy of these separators is a result of the dry technique used to manufacture the micro-porous membranes. Separators prepared using the wet technique (Entek Gold LP) behaved more uniformly, or biaxially, where all mechanical properties were nearly identical within the separator plane. The information provided by the DMA can also be useful for predicting the long-term durability of polymer separators in lithium-ion batteries exposed to electrolyte (solvent and salt), thermal fluctuations and electrochemical cycling. Small losses in mechanical integrity were observed for separators exposed to the various immersion environments over the 4-week immersion time.

Phase Behavior of Binary Blends of AB+AC Block Copolymers with compatible B and C blocks

NASA Astrophysics Data System (ADS)

Pryamitsyn, Victor; Ganesan, Venkat

2012-02-01

Recently the experimental studies of phase behavior of binary blends of PS-b-P2VP and PS-b-PHS demonstrated an interesting effect: blends of symmetric PS-b-P2VP and shorter symmetric (PS-b-PHS) formed cylindrical HEX and spherical BCC phases, while each pure component formed lamellas. The miscibility of P2VP and PHS is caused by the hydrogen bonding between P2VP and PHS,which can be described as a negative Flory ?-parameter between P2VP and PHS. We developed a theory of the microphase segregation of AB+AC blends of diblock copolymers based on strong stretching theory. The main result of our theory is that in the copolymer brush-like layer formed by longer B chain and shorter C chains, the attraction between B and shorter C chains causes relative stretching of short C chains and compression of longer B chains. The latter manifests in an excessive bending force towards the grafting surface (BC|AA interface). Such bending force causes a transition from a symmetric lamella phase to a HEX cylinder or BCC spherical phases with the BC phase being a ``matrix'' component. In a blend of asymmetric BCC sphere forming copolymers (where B and C segments are the minor components), such bending force may unfold BCC spherical phase to a HEX cylinder phase, or even highly uneven lamella phases.

A preliminary investigation of boundary-layer transition along a flat plate with adverse pressure gradient

NASA Technical Reports Server (NTRS)

Von Doenhoff, Albert E

1938-01-01

Boundary-layer surveys were made throughout the transition region along a smooth flat plate placed in an airstream of practically zero turbulence and with an adverse pressure gradient. The boundary-layer Reynolds number at the laminar separation point was varied from 1,800 to 2,600. The test data, when considered in the light of certain theoretical deductions, indicated that transition probably began with separation of the laminar boundary layer. The extent of the transition region, defined as the distance from a calculated laminar separation point to the position of the first fully developed turbulent boundary-layer profile, could be expressed as a constant Reynolds number run of approximately 70,000. Some speculations are presented concerning the application of the foregoing concepts, after certain assumptions have been made, to the problem of the connection between transition on the upper surface of an airfoil at high angles of attack and the maximum lift.

The Role of Separation Bubbles on the Aerodynamic Characteristics of Airfoils, Including Stall and Post-Stall, at Low Reynolds Numbers

NASA Technical Reports Server (NTRS)

Chen, Hsun H.; Cebeci, Tuncer

2007-01-01

Airfoils at high Reynolds numbers, in general, have small separation bubbles that are usually confined to the leading edge. Since the Reynolds number is large, the turbulence model for the transition region between the laminar and turbulent flow is not important. Furthermore, the onset of transition occurs either at separation or prior to separation and can be predicted satisfactorily by empirical correlations when the incident angle is small and can be assumed to correspond to laminar separation when the correlations do not apply, i.e., at high incidence angles.

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

Schmitt, Adam K.; Mahanthappa, Mahesh K.

Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), we document the composition-dependent morphologies of 39 new poly(lactide-block-1,4-butadiene-block-lactide) (LBL) block polymers, comprising a broad dispersity B segment (Mn = 4.5–17.7 kg/mol;more » $$\\def\\eth{{\\specialfont\\char238}}$$ = Mw/Mn = 1.72–1.88) and narrow dispersity L end blocks (Mn = 0.6–15.3 kg/mol; $$\\def\\eth{{\\specialfont\\char238}}$$ = 1.10–1.21) with volume fractions 0.26 ≤ fB ≤ 0.95. A subset of these samples undergo melt self-assembly into cylindrical, lamellar, and apparently bicontinuous morphologies. By assessing the states of order and disorder in these triblock polymer melts using temperature-dependent SAXS, we find that broad B segment dispersity increases the minimum segregation strength χN ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction χN ≥ 17.9 for narrow dispersity analogues. While B segment dispersity has previously been shown to thermodynamically stabilize the self-assembled morphologies of low χ/high N ABA triblocks, the present study indicates that broad B block dispersity in related high χ/low N systems destabilizes the microphase-separated melt. These observations are rationalized in terms of recent theories that suggest that broad segmental dispersity substantially enhances fluctuation effects at low N, thus disfavoring melt segregation.« less

DNA-nanoparticle assemblies go organic: macroscopic polymeric materials with nanosized features.

PubMed

Mentovich, Elad D; Livanov, Konstantin; Prusty, Deepak K; Sowwan, Mukules; Richter, Shachar

2012-05-30

One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC), which creates an all-organic engineered network.

Organic-inorganic random copolymers from methacrylate-terminated poly(ethylene oxide) with 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane: synthesis via RAFT polymerization and self-assembly behavior.

PubMed

Wei, Kun; Li, Lei; Zheng, Sixun; Wang, Ge; Liang, Qi

2014-01-14

In this contribution, we report the synthesis of organic-inorganic random polymers from methacrylate-terminated poly(ethylene oxide) (MAPEO) (Mn = 950) and 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MAPOSS) macromers via reversible addition-fragmentation chain transfer (RAFT) polymerization with 4-cyano-4-(thiobenzoylthio) valeric acid (CTBTVA) as the chain transfer agent. The organic-inorganic random copolymers were characterized by means of (1)H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results of GPC indicate that the polymerizations were carried out in a controlled fashion. Transmission electron microscopy (TEM) showed that the organic-inorganic random copolymers in bulk were microphase-separated and the POSS microdomains were formed via POSS-POSS interactions. In aqueous solutions the organic-inorganic random copolymers were capable of self-assembling into spherical nanoobjects as evidenced by transmission electron microscopy (TEM) and dynamic laser scattering (DLS). The self-assembly behavior of the organic-inorganic random copolymers was also found to occur in the mixtures with the precursors of epoxy. The nanostructures were further fixed via subsequent curing reaction and thus the organic-inorganic nanocomposites were obtained. The formation of nanophases in epoxy thermosets was confirmed by transmission electron microscopy (TEM) and dynamic mechanical thermal analysis (DMTA). The organic-inorganic nanocomposites displayed the enhanced surface hydrophobicity as evidenced by surface contact angle measurements.

Thermal crystallization mechanism of silk fibroin protein

NASA Astrophysics Data System (ADS)

Hu, Xiao

In this thesis, the thermal crystallization mechanism of silk fibroin protein from Bombyx mori silkworm, was treated as a model for the general study of protein based materials, combining theories from both biophysics and polymer physics fields. A systematic and scientific path way to model the dynamic beta-sheet crystallization process of silk fibroin protein was presented in the following sequence: (1) The crystallinity, fractions of secondary structures, and phase compositions in silk fibroin proteins at any transition stage were determined. Two experimental methods, Fourier transform infrared spectroscopy (FTIR) with Fourier self-deconvolution, and specific reversing heat capacity, were used together for the first time for modeling the static structures and phases in the silk fibroin proteins. The protein secondary structure fractions during the crystallization were quantitatively determined. The possibility of existence of a "rigid amorphous phase" in silk protein was also discussed. (2) The function of bound water during the crystallization process of silk fibroin was studied using heat capacity, and used to build a silk-water dynamic crystallization model. The fundamental concepts and thermal properties of silk fibroin with/without bound water were discussed. Results show that intermolecular bound water molecules, acting as a plasticizer, will cause silk to display a water-induced glass transition around 80°C. During heating, water is lost, and the change of the microenvironment in the silk fibroin chains induces a mesophase prior to thermal crystallization. Real time FTIR during heating and isothermal holding above Tg show the tyrosine side chain changes only during the former process, while beta sheet crystallization occurs only during the latter process. Analogy is made between the crystallization of synthetic polymers according to the four-state scheme of Strobl, and the crystallization process of silk fibroin, which includes an intermediate precursor stage before crystallization. (3) The beta-sheet crystallization kinetics in silk fibroin protein were measured using X-ray, FTIR and heat flow, and the structure reveals the formation mechanism of the silk crystal network. Avrami kinetics theories, which were established for studies of synthetic polymer crystal growth, were for the first time extended to investigate protein self-assembly in multiblock silk fibroin samples. The Avrami exponent, n, was close to two for all methods, indicating formation of beta sheet crystals in silk proteins is different from the 3-D spherulitic crystal growth found in most synthetic homopolymers. A microphase separation pattern after chymotrypsin enzyme biodegradation was shown in the protein structures using scanning electron microscopy. A model was then used to explain the crystallization of silk fibroin protein by analogy to block copolymers. (4) The effects of metal ions during the crystallization of silk fibroin was investigated using thermal analysis. Advanced thermal analysis methods were used to analyze the thermal protein-metallic ion interactions in silk fibroin proteins. Results show that K+ and Ca2+ metallic salts play different roles in silk fibroin proteins, which either reduce (K+) or increase (Ca2+ ) the glass transition (Tg) of pure silk protein and affect the thermal stability of this structure.

Transition scenario and transition control of the flow over a semi-infinite square leading-edge plate

NASA Astrophysics Data System (ADS)

Huang, Yadong; Zhou, Benmou; Tang, Zhaolie; Zhang, Fei

2017-07-01

In recent investigations of the flow over a square leading-edge flat plate, elliptic instability and transient growth of perturbations are proposed to explain the turbulent transition mechanism of the separating and reattaching flow reported in early experimental visualizations. An original transition scenario as well as a transition control method is presented by a detailed numerical study in this paper. The transient growth of perturbations in the separation bubble induces the primary instability that causes the 2D unsteady flow consisting of Kelvin-Helmholtz (KH) vortices. The pairing instability of the KH vortices induces the subharmonic secondary instability, and then resonance transition occurs. The streamwise Lorentz force as the control input is applied in the recirculation region where the separation bubble generates. The maximum energy amplification magnitude of perturbations takes a linear attenuation with the interaction number; thus, the primary instability is reduced under control. The interaction number represents the strength of the streamwise Lorentz force relative to the inertial force of the fluid. The reduced primary instability is not strong enough to induce the secondary instability, so the flow is globally stable under control. Three-dimensional direct numerical simulation confirms the results of the linear stability analysis. Although the growth rate of the convectively unstable secondary instability is limited by the flow field scale, the feedback loop of the energy transfer promotes the resonance transition. However, as the separation bubble scale is reduced and the feedback loop is broken by the streamwise Lorentz force, the three-dimensional transition is suppressed and a skin-friction drag reduction is achieved.

Structure of polyacrylic acid and polymethacrylic acid solutions : a small angle neutron scattering study

NASA Astrophysics Data System (ADS)

Moussaid, A.; Schosseler, F.; Munch, J. P.; Candau, S. J.

1993-04-01

The intensity scattered from polyacrylic acid and polymethacrylic acid solutions has been measured by small angle neutron scattering experiemnts. The influence of polymer concentration, ionization degree, temperature and salt content has been investigated. Results are in qualitative agreement with a model which predicts the existence of microphases in the unstable region of the phase diagram. Quantitative comparison with the theory is performed by fitting the theoretical structure factor to the experimental data. For a narrow range of ionizaiton degrees nearly quantitative agreement with the theory is found for the polyacrylic acide system.

Boundary-Layer Separation Control under Low-Pressure Turbine Airfoil Conditions using Glow-Discharge Plasma Actuators

NASA Technical Reports Server (NTRS)

Hultgren, Lennart S.; Ashpis, David E.

2003-01-01

Modem low-pressure turbines, in general, utilize highly loaded airfoils in an effort to improve efficiency and to lower the number of airfoils needed. Typically, the airfoil boundary layers are turbulent and fully attached at takeoff conditions, whereas a substantial fraction of the boundary layers on the airfoils may be transitional at cruise conditions due to the change of density with altitude. The strong adverse pressure gradients on the suction side of these airfoils can lead to boundary-layer separation at the latter low Reynolds number conditions. Large separation bubbles, particularly those which fail to reattach, cause a significant degradation of engine efficiency. A component efficiency drop of the order 2% may occur between takeoff and cruise conditions for large commercial transport engines and could be as large as 7% for smaller engines at higher altitude. An efficient means of of separation elimination/reduction is, therefore, crucial to improved turbine design. Because the large change in the Reynolds number from takeoff to cruise leads to a distinct change in the airfoil flow physics, a separation control strategy intended for cruise conditions will need to be carefully constructed so as to incur minimum impact/penalty at takeoff. A complicating factor, but also a potential advantage in the quest for an efficient strategy, is the intricate interplay between separation and transition for the situation at hand. Volino gives a comprehensive discussion of several recent studies on transition and separation under low-pressure-turbine conditions, among them one in the present facility. Transition may begin before or after separation, depending on the Reynolds number and other flow conditions. If the transition occurs early in the boundary layer then separation may be reduced or completely eliminated. Transition in the shear layer of a separation bubble can lead to rapid reattachment. This suggests using control mechanisms to trigger and enhance early transition. Gad-el-Hak provides a review of various techniques for flow control in general and Volino discusses recent studies on separation control under low-pressure-turbine conditions utilizing passive as well as active devices. As pointed out by Volino, passive devices optimized for separation control at low Reynolds numbers tend to increase losses at high Reynolds numbers, Active devices have the attractive feature that they can be utilized only in operational regimes where they are needed and when turned off would not affect the flow. The focus in the present paper is an experimental Separation is induced on a flat plate installed in a closed-circuit wind tunnel by a shaped insert on the opposite wall. The flow conditions represent flow over the suction surface of a modem low-pressure-turbine airfoil ('Pak-B'). The Reynolds number, based on wetted plate length and nominal exit velocity, is varied from 50,000 to 300,000, covering cruise to takeoff conditions. Low (0.2%) and high (2.5%) Gee-stream turbulence intensities are set using passive grids. A spanwise-oriented phased-plasma-array actuator, fabricated on a printed circuit board, is surface- flush-mounted upstream of the separation point and can provide forcing in a wide frequency range. Static surface pressure measurements and hot-wire anemometry of the base and controlled flows are performed and indicate that the glow-discharge plasma actuator is an effective device for separation control. of active separation control using glow discharge plasma actuators.

Particles decorated by an ionizable thermoresponsive polymer brush in water: experiments and self-consistent field modeling.

PubMed

Alves, S P C; Pinheiro, J P; Farinha, J P S; Leermakers, F A M

2014-03-20

We have synthesized anionic multistimuli responsive core-shell polymer nanoparticles with low size dispersity composed of glassy poly(methyl methacrylate) (PMMA) cores of ca. 40 nm radius and poly(N-isopropylacrylamide) (PNIPAM) anionic brush-like shells with methacrylic acid comonomers. Using dynamic light scattering, we observed a volume phase transition upon an increase in temperature and this response was pH and ionic strength dependent. Already at room temperature we observed a pronounced polyelectrolyte effect, that is, a shift of the apparent pKa extracted from the degree of dissociation of the acids as a function of the pH. The multiresponsive behavior of the hydrophobic polyelectrolyte brush has been modeled using the Scheutjens-Fleer self-consistent field (SF-SCF) approach. Using a phenomenological relation between the Flory-Huggins χ parameter and the temperature, we confront the predicted change in the brush height with the observed change of the hydrodynamic radius and degree of dissociation and obtain estimates for the average chain lengths (number of Kuhn segments) of the corona chains, the grafting density and charge density distributions. The theory reveals a rich internal structure of the hydrophobic polyelectrolyte brush, especially near the collapse transition, where we find a microphase segregated structure. Considering this complexity, it is fair to state that the theoretical predictions follow the experimental data semiquantitatively, and it is attractive to attribute the observed disparity between theory and experiments to the unknown polydispersity of the chains, the unknown distribution of the charges, or other experimental complications. More likely, however, the deviations point to significant problems of the mean field theory, which focuses solely on the radial distributions and ignores the possibility of the formation of lateral (local) inhomogeneities in partially collapsed polyelectrolyte brushes. We argue that the PNIPAM brush at room temperature is already behaving nonideally.

Effects of free-stream turbulence intensity on transition in a laminar separation bubble formed over an airfoil

NASA Astrophysics Data System (ADS)

Istvan, Mark S.; Yarusevych, Serhiy

2018-03-01

The laminar-to-turbulent transition process in a laminar separation bubble formed over a NACA 0018 airfoil is investigated experimentally. All experiments are performed for an angle of attack of 4°, chord Reynolds numbers of 80,000 and 125,000, and free-stream turbulence intensities between 0.06 and 1.99%. The results show that increasing the level of free-stream turbulence intensity leads to a decrease in separation bubble length, attributed to a downstream shift in mean separation and an upstream shift in mean reattachment, the later ascribed to an upstream shift in mean transition. Maximum spatial amplification rates of disturbances in the separated shear layer decrease with increasing free-stream turbulence intensity, implying that the larger initial amplitudes of disturbances are solely responsible for the upstream shift in mean transition and as a result mean reattachment. At the baseline level of turbulence intensity, coherent structures forming in the aft portion of the bubble are characterized by strong spanwise coherence at formation, and undergo spanwise deformations leading to localized breakup in the vicinity of mean reattachment. As the level of free-stream turbulence intensity is increased, the spanwise coherence of the shear layer rollers is reduced, and spanwise undulations in the vortex filaments start to take place at the mean location of roll-up. At the highest level of turbulence intensity investigated, streamwise streaks originating in the boundary layer upstream of the separation bubble are observed within the bubble. These streaks signify an onset of bypass transition upstream of the separation bubble, which gives rise to a highly three-dimensional shear layer roll-up. A quantitative analysis of the associated changes in salient characteristics of the coherent structures is presented, connecting the effect of elevated free-stream turbulence intensity on the time-averaged and dynamic characteristics of the separation bubble.

Rouse-Bueche Theory and The Calculation of The Monomeric Friction Coefficient in a Filled System

NASA Astrophysics Data System (ADS)

Martinetti, Luca; Macosko, Christopher; Bates, Frank

According to flexible chain theories of viscoelasticity, all relaxation and retardation times of a polymer melt (hence, any dynamic property such as the diffusion coefficient) depend on the monomeric friction coefficient, ζ0, i.e. the average drag force per monomer per unit velocity encountered by a Gaussian submolecule moving through its free-draining surroundings. Direct experimental access to ζ0 relies on the availability of a suitable polymer dynamics model. Thus far, no method has been suggested that is applicable to filled systems, such as filled rubbers or microphase-segregated A-B-A thermoplastic elastomers at temperatures where one of the blocks is glassy. Building upon the procedure proposed by Ferry for entangled and unfilled polymer melts, the Rouse-Bueche theory is applied to an undiluted triblock copolymer to extract ζ0 from the linear viscoelastic behavior in the rubber-glass transition region, and to estimate the size of Gaussian submolecules. At iso-free volume conditions, the so-obtained matrix monomeric friction factor is consistent with the corresponding value for the homopolymer melt. In addition, the characteristic Rouse dimensions are in good agreement with independent estimates based on the Kratky-Porod worm-like chain model. These results seem to validate the proposed approach for estimating ζ0 in a filled system. Although preliminary tested on a thermoplastic elastomer of the A-B-A type, the method may be extended and applied to filled homopolymers as well.

Flow Control on Low-Pressure Turbine Airfoils Using Vortex Generator Jets

NASA Technical Reports Server (NTRS)

Volino, Ralph J.; Ibrahim, Mounir B.; Kartuzova, Olga

2010-01-01

Motivation - Higher loading on Low-Pressure Turbine (LPT) airfoils: Reduce airfoil count, weight, cost. Increase efficiency, and Limited by suction side separation. Growing understanding of transition, separation, wake effects: Improved models. Take advantage of wakes. Higher lift airfoils in use. Further loading increases may require flow control: Passive: trips, dimples, etc. Active: plasma actuators, vortex generator jets (VGJs). Can increased loading offset higher losses on high lift airfoils. Objectives: Advance knowledge of boundary layer separation and transition under LPT conditions. Demonstrate, improve understanding of separation control with pulsed VGJs. Produce detailed experimental data base. Test and develop computational models.

10 CFR 5.230 - Transition plans.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 1 2014-01-01 2014-01-01 false Transition plans. 5.230 Section 5.230 Energy NUCLEAR... FEDERAL FINANCIAL ASSISTANCE Coverage § 5.230 Transition plans. (a) Submission of plans. An institution to... either a single transition plan applicable to all such units, or a separate transition plan applicable to...

10 CFR 5.230 - Transition plans.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 1 2012-01-01 2012-01-01 false Transition plans. 5.230 Section 5.230 Energy NUCLEAR... FEDERAL FINANCIAL ASSISTANCE Coverage § 5.230 Transition plans. (a) Submission of plans. An institution to... either a single transition plan applicable to all such units, or a separate transition plan applicable to...

10 CFR 5.230 - Transition plans.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 1 2011-01-01 2011-01-01 false Transition plans. 5.230 Section 5.230 Energy NUCLEAR... FEDERAL FINANCIAL ASSISTANCE Coverage § 5.230 Transition plans. (a) Submission of plans. An institution to... either a single transition plan applicable to all such units, or a separate transition plan applicable to...

10 CFR 5.230 - Transition plans.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 1 2013-01-01 2013-01-01 false Transition plans. 5.230 Section 5.230 Energy NUCLEAR... FEDERAL FINANCIAL ASSISTANCE Coverage § 5.230 Transition plans. (a) Submission of plans. An institution to... either a single transition plan applicable to all such units, or a separate transition plan applicable to...

29 CFR 36.230 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 1 2010-07-01 2010-07-01 true Transition plans. 36.230 Section 36.230 Labor Office of the... FEDERAL FINANCIAL ASSISTANCE Coverage § 36.230 Transition plans. (a) Submission of plans. An institution... submit either a single transition plan applicable to all such units, or a separate transition plan...

10 CFR 5.230 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 10 Energy 1 2010-01-01 2010-01-01 false Transition plans. 5.230 Section 5.230 Energy NUCLEAR... FEDERAL FINANCIAL ASSISTANCE Coverage § 5.230 Transition plans. (a) Submission of plans. An institution to... either a single transition plan applicable to all such units, or a separate transition plan applicable to...

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, Michael A.; Hallen, Richard T.

1990-01-01

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, M.A.; Hallen, R.T.

1991-10-15

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, M.A.; Hallen, R.T.

1990-08-28

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, Michael A.; Hallen, Richard T.

1991-01-01

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

Minnowbrook IV: 2003 Workshop on Transition and Unsteady Aspects of Turbomachinery Flows

NASA Technical Reports Server (NTRS)

LaGraff, John E. (Editor); Ashpis, David E.

2004-01-01

This Minnowbrook IV 2003 workshop on Transition and Unsteady Aspects of Turbomachinery Flows includes the following topics: 1) Current Issues in Unsteady Turbomachinery Flows; 2) Global Instability and Control of Low-Pressure Turbine Flows; 3) Influence of End Wall Leakage on Secondary Flow Development in Axial Turbines; 4) Active and Passive Flow Control on Low Pressure Turbine Airfoils; 5) Experimental and Numerical Investigation of Transitional Flows as Affected by Passing Wakes; 6) Effects of Freestream Turbulence on Turbine Blade Heat Transfer; 7) Bypass Transition Via Continuous Modes and Unsteady Effects on Film Cooling; 8) High Frequency Surface Heat Flux Imaging of Bypass Transition; 9) Skin Friction and Heat Flux Oscillations in Upstream Moving Wave Packets; 10) Transition Mechanisms and Use of Surface Roughness to Enhance the Benefits of Wake Passing in LP Turbines; 11) Transient Growth Approach to Roughness-Induced Transition; 12) Roughness- and Freestream-Turbulence-Induced Transient Growth as a Bypass Transition Mechanism; 13) Receptivity Calculations as a Means to Predicting Transition; 14) On Streamwise Vortices in a Curved Wall Jet and Their Effect on the Mean Flow; 15) Plasma Actuators for Separation Control of Low Pressure Turbine Blades; 16) Boundary-Layer Separation Control Under Low-Pressure-Turbine Conditions Using Glow-Discharge Plasma Actuators; 17) Control of Separation for Low Pressure Turbine Blades: Numerical Simulation; 18) Effects of Elevated Free-Stream Turbulence on Active Control of a Separation Bubble; 19) Wakes, Calming and Transition Under Strong Adverse Pressure Gradients; 20) Transitional Bubble in Periodic Flow Phase Shift; 21) Modelling Spots: The Calmed Region, Pressure Gradient Effects and Background; 22) Modeling of Unsteady Transitional Flow on Axial Compressor Blades; 23) Challenges in Predicting Component Efficiencies in Turbomachines With Low Reynolds Number Blading; 24) Observations on the Causal Relationship Between Blade Count and Developing Rotating Stall in a Four Stage Axial Compressor; 25) Experimental and Numerical Study of Non-Linear Interactions in Transonic Nozzle Flow; 26) Clocking Effects on a Modern Stage and One-Half Transonic Turbine; 27) DNS and LES of Transition on Turbine Blades; 28) The Use of Cellular Automata in Modeling the Transition; 29) Predicting Unsteady Buffet Onset Using RANS Solutions; 30) Transition Modelling With the SST Turbulence Model and an Intermittency Transport; and 31) Equation Workshop Summary Transcript

Two-component Gaussian core model: Strong-coupling limit, Bjerrum pairs, and gas-liquid phase transition.

PubMed

Frydel, Derek; Levin, Yan

2018-01-14

In the present work, we investigate a gas-liquid transition in a two-component Gaussian core model, where particles of the same species repel and those of different species attract. Unlike a similar transition in a one-component system with particles having attractive interactions at long separations and repulsive interactions at short separations, a transition in the two-component system is not driven solely by interactions but by a specific feature of the interactions, the correlations. This leads to extremely low critical temperature, as correlations are dominant in the strong-coupling limit. By carrying out various approximations based on standard liquid-state methods, we show that a gas-liquid transition of the two-component system poses a challenging theoretical problem.

Two-component Gaussian core model: Strong-coupling limit, Bjerrum pairs, and gas-liquid phase transition

NASA Astrophysics Data System (ADS)

Frydel, Derek; Levin, Yan

2018-01-01

In the present work, we investigate a gas-liquid transition in a two-component Gaussian core model, where particles of the same species repel and those of different species attract. Unlike a similar transition in a one-component system with particles having attractive interactions at long separations and repulsive interactions at short separations, a transition in the two-component system is not driven solely by interactions but by a specific feature of the interactions, the correlations. This leads to extremely low critical temperature, as correlations are dominant in the strong-coupling limit. By carrying out various approximations based on standard liquid-state methods, we show that a gas-liquid transition of the two-component system poses a challenging theoretical problem.

Photocurrent spectroscopy of exciton and free particle optical transitions in suspended carbon nanotube pn-junctions

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

Chang, Shun-Wen; Theiss, Jesse; Hazra, Jubin

2015-08-03

We study photocurrent generation in individual, suspended carbon nanotube pn-junction diodes formed by electrostatic doping using two gate electrodes. Photocurrent spectra collected under various electrostatic doping concentrations reveal distinctive behaviors for free particle optical transitions and excitonic transitions. In particular, the photocurrent generated by excitonic transitions exhibits a strong gate doping dependence, while that of the free particle transitions is gate independent. Here, the built-in potential of the pn-junction is required to separate the strongly bound electron-hole pairs of the excitons, while free particle excitations do not require this field-assisted charge separation. We observe a sharp, well defined E{sub 11}more » free particle interband transition in contrast with previous photocurrent studies. Several steps are taken to ensure that the active charge separating region of these pn-junctions is suspended off the substrate in a suspended region that is substantially longer than the exciton diffusion length and, therefore, the photocurrent does not originate from a Schottky junction. We present a detailed model of the built-in fields in these pn-junctions, which, together with phonon-assistant exciton dissociation, predicts photocurrents on the same order of those observed experimentally.« less

26 CFR 1.985-6 - Transition rules for a QBU that uses the dollar approximate separate transactions method for its...

Code of Federal Regulations, 2010 CFR

2010-04-01

... section sets forth transition rules for a QBU that used the dollar approximate separate transactions... QBU must determine the dollar and hyperinflationary currency basis of its assets and the dollar and hyperinflationary currency amount of its liabilities that were acquired or incurred in taxable years beginning...

18 CFR 1317.230 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 18 Conservation of Power and Water Resources 2 2010-04-01 2010-04-01 false Transition plans. 1317... Coverage § 1317.230 Transition plans. (a) Submission of plans. An institution to which § 1317.225 applies... transition plan applicable to all such units, or a separate transition plan applicable to each such unit. (b...

Predictions of Separated and Transitional Boundary Layers Under Low-Pressure Turbine Airfoil Conditions Using an Intermittency Transport Equation

NASA Technical Reports Server (NTRS)

Suzen, Y. Bora; Huang, P. G.; Hultgren, Lennart S.; Ashpis, David E.

2001-01-01

A new transport equation for the intermittency factor was proposed to predict separated and transitional boundary layers under low-pressure turbine airfoil conditions. The intermittent behavior of the transitional flows is taken into account and incorporated into computations by modifying the eddy viscosity, mu(sub t), with the intermittency factor, gamma. Turbulent quantities are predicted by using Menter's two-equation turbulence model (SST). The intermittency factor is obtained from a transport equation model, which not only can reproduce the experimentally observed streamwise variation of the intermittency in the transition zone, but also can provide a realistic cross-stream variation of the intermittency profile. In this paper, the intermittency model is used to predict a recent separated and transitional boundary layer experiment under low pressure turbine airfoil conditions. The experiment provides detailed measurements of velocity, turbulent kinetic energy and intermittency profiles for a number of Reynolds numbers and freestream turbulent intensity conditions and is suitable for validation purposes. Detailed comparisons of computational results with experimental data are presented and good agreements between the experiments and predictions are obtained.

Predictions of Separated and Transitional Boundary Layers Under Low-Pressure Turbine Airfoil Conditions Using an Intermittency Transport Equation

NASA Technical Reports Server (NTRS)

Suzen, Y. B.; Huang, P. G.; Hultgren, Lennart S.; Ashpis, David E.

2003-01-01

A new transport equation for the intermittency factor was proposed to predict separated and transitional boundary layers under low-pressure turbine airfoil conditions. The intermittent behavior of the transitional flows is taken into account and incorporated into computations by modifying the eddy viscosity, t , with the intermittency factor, y. Turbulent quantities are predicted by using Menter s two-equation turbulence model (SST). The intermittency factor is obtained from a transport equation model, which not only can reproduce the experimentally observed streamwise variation of the intermittency in the transition zone, but also can provide a realistic cross-stream variation of the intermittency profile. In this paper, the intermittency model is used to predict a recent separated and transitional boundary layer experiment under low pressure turbine airfoil conditions. The experiment provides detailed measurements of velocity, turbulent kinetic energy and intermittency profiles for a number of Reynolds numbers and freestream turbulent intensity conditions and is suitable for validation purposes. Detailed comparisons of computational results with experimental data are presented and good agreements between the experiments and predictions are obtained.

Transient Three-Dimensional Analysis of Side Load in Liquid Rocket Engine Nozzles

NASA Technical Reports Server (NTRS)

Wang, Ten-See

2004-01-01

Three-dimensional numerical investigations on the nozzle start-up side load physics were performed. The objective of this study is to identify the three-dimensional side load physics and to compute the associated aerodynamic side load using an anchored computational methodology. The computational methodology is based on an unstructured-grid, and pressure-based computational fluid dynamics formulation, and a simulated inlet condition based on a system calculation. Finite-rate chemistry was used throughout the study so that combustion effect is always included, and the effect of wall cooling on side load physics is studied. The side load physics captured include the afterburning wave, transition from free- shock to restricted-shock separation, and lip Lambda shock oscillation. With the adiabatic nozzle, free-shock separation reappears after the transition from free-shock separation to restricted-shock separation, and the subsequent flow pattern of the simultaneous free-shock and restricted-shock separations creates a very asymmetric Mach disk flow. With the cooled nozzle, the more symmetric restricted-shock separation persisted throughout the start-up transient after the transition, leading to an overall lower side load than that of the adiabatic nozzle. The tepee structures corresponding to the maximum side load were addressed.

Contactless electroreflectance studies of free exciton binding energy in Zn1-xMgxO epilayers

NASA Astrophysics Data System (ADS)

Wełna, M.; Kudrawiec, R.; Kaminska, A.; Kozanecki, A.; Laumer, B.; Eickhoff, M.; Misiewicz, J.

2013-12-01

Contactless electroreflectance (CER) has been applied to study optical transitions in Zn1-xMgxO layers with magnesium concentration ≤44%. CER resonances related to free exciton and band-to-band transitions were clearly observed at room temperature. For ZnO the two transitions are separated by the energy of ˜65 meV, which is attributed to the free exciton binding energy in ZnO. Due to magnesium incorporation, the CER resonances broaden and shift to blue. The energy separation between excitonic and band-to-band transitions increases up to ˜100 meV when the magnesium concentration reaches 22%. For larger magnesium concentrations, CER resonances are significantly broadened and the excitonic transition is no longer resolved in the CER spectrum.

High temperature lithium cells with solid polymer electrolytes

DOEpatents

Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

2017-03-07

Electrochemical cells that use electrolytes made from new polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers. Such electrochemical cells can operate safely at higher temperatures than have been possible before, especially in lithium cells. The ionic conductivity of the electrolytes increases with increasing temperature.

Compendium of Programs to Assist the Transition

DTIC Science & Technology

1993-02-01

Program Description The Interagency Placement Assistance Program (IPAP) offices maintain computerized listings of data on employees faced with...possible reduction in force (RIF) separations. Program Objective To provide placement assistance to employees faced with possible RIF separations by making... employees . 23 2/93 TRANSITION ASSISTANCE PROGRAM Short Name of Program TAP Program Description Begun in 1991, TAP is a joint program of

Calibration of a γ- Re θ transition model and its application in low-speed flows

NASA Astrophysics Data System (ADS)

Wang, YunTao; Zhang, YuLun; Meng, DeHong; Wang, GunXue; Li, Song

2014-12-01

The prediction of laminar-turbulent transition in boundary layer is very important for obtaining accurate aerodynamic characteristics with computational fluid dynamic (CFD) tools, because laminar-turbulent transition is directly related to complex flow phenomena in boundary layer and separated flow in space. Unfortunately, the transition effect isn't included in today's major CFD tools because of non-local calculations in transition modeling. In this paper, Menter's γ- Re θ transition model is calibrated and incorporated into a Reynolds-Averaged Navier-Stokes (RANS) code — Trisonic Platform (TRIP) developed in China Aerodynamic Research and Development Center (CARDC). Based on the experimental data of flat plate from the literature, the empirical correlations involved in the transition model are modified and calibrated numerically. Numerical simulation for low-speed flow of Trapezoidal Wing (Trap Wing) is performed and compared with the corresponding experimental data. It is indicated that the γ- Re θ transition model can accurately predict the location of separation-induced transition and natural transition in the flow region with moderate pressure gradient. The transition model effectively imporves the simulation accuracy of the boundary layer and aerodynamic characteristics.

Chimeric Plastics : a new class of thermoplastic

NASA Astrophysics Data System (ADS)

Sonnenschein, Mark

A new class of thermoplastics (dubbed ``Chimerics'') is described that exhibits a high temperature glass transition followed by high performance elastomer properties, prior to melting. These transparent materials are comprised of co-continuous phase-separated block copolymers. One block is an amorphous glass with a high glass transition temperature, and the second is a higher temperature phase transition block creating virtual thermoreversible crosslinks. The material properties are highly influenced by phase separation on the order of 10-30 nanometers. At lower temperatures the polymer reflects the sum of the block copolymer properties. As the amorphous phase glass transition is exceeded, the virtual crosslinks of the higher temperature second phase dominate the plastic properties, resulting in rubber-like elasticity.

31 CFR 28.230 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 1 2010-07-01 2010-07-01 false Transition plans. 28.230 Section 28... Transition plans. (a) Submission of plans. An institution to which § 28.225 applies and that is composed of more than one administratively separate unit may submit either a single transition plan applicable to...

Synthesis and characterization of ion containing polymers

NASA Astrophysics Data System (ADS)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 < alpha < 0.6) and counterions (Cl- and I-) were investigated in good solvent (EG, NMF, and GC) and poor solvent (DW and F). The concentration dependence of the specific viscosity and relaxation time of polyelectrolytes in solution agrees with Dobrynin's theoretical predictions at c < c**. Effective charge density greatly impacts the viscosity of polyelectrolyte semidilute solutions, while residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c < 2cs/f. For polyelectrolyte solutions with less condensed counterions, the correlation length obtained from SAXS and rheology perfectly matches and agrees with de Gennes prediction. Dobrynin scaling model successfully predicts the rheology of polyelectrolyte solutions in all cases: without salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

DNA-nanoparticle assemblies go organic: Macroscopic polymeric materials with nanosized features

PubMed Central

2012-01-01

Background One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. Method Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. Results and conclusions One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC), which creates an all-organic engineered network. PMID:22646980

Inhibition and Promotion of Heat-Induced Gelation of Whey Proteins in the Presence of Calcium by Addition of Sodium Caseinate.

PubMed

Nguyen, Bach T; Balakrishnan, Gireeshkumar; Jacquette, Boris; Nicolai, Taco; Chassenieux, Christophe; Schmitt, Christophe; Bovetto, Lionel

2016-11-14

Heat-induced aggregation and gelation of aqueous solutions of whey protein isolate (WPI) in the presence of sodium caseinate (SC) and CaCl 2 was studied at pH 6.6. The effect of adding SC (0-100 g/L) on the structure of the aggregates and the gels was investigated by light scattering and confocal laser scanning microscopy at different CaCl 2 concentration ([CaCl 2 ] = 0-30 mM). The gelation process was studied by oscillatory shear rheology. At the whey protein concentrations studied here (34 and 60 g/L), no gels were formed in the absence of CaCl 2 and SC. However, WPI solutions gelled above a critical CaCl 2 concentration that increased with increasing SC concentration. In the absence of CaCl 2 , WPI gels were formed only above a critical SC concentration. The critical SC concentration needed to induce WPI gelation decreased weakly when CaCl 2 was added. In an intermediate range of CaCl 2 concentrations, gels were formed both at low and high SC concentrations, but not at intermediate SC concentrations. Finally, at high CaCl 2 concentrations gels were formed at all SC concentrations. The gelation rate and the gel structure of the gels formed at low and high casein concentrations were very different. The effect of SC on the thermal gelation of WPI was interpreted by competition for Ca 2+ , a chaperon effect, and microphase separation.

Facile synthesis of functional polyperoxides by radical alternating copolymerization of 1,3-dienes with oxygen.

PubMed

Sato, Eriko; Matsumoto, Akikazu

2009-01-01

We have developed a facile synthesis of degradable polyperoxides by the radical alternating copolymerization of 1,3-diene monomers with molecular oxygen at an atmospheric pressure. In this review, the synthesis, the degradation behavior, and the applications of functional polyperoxides are summarized. The alkyl sorbates as the conjugated 1,3-dienes gave a regiospecific alternating copolymer by exclusive 5,4-addition during polymerization and the resulting polyperoxides decomposed by the homolysis of a peroxy linkage followed by successive beta-scissions. The preference of 5,4-addition was well rationalized by theoretical calculations. The degradation of the polyperoxides occurred with various stimuli, such as heating, UV irradiation, a redox reaction with amines, and an enzyme reaction. The various functional polyperoxides were synthesized by following two methods, one is the direct copolymerization of functional 1,3-dienes, and the other is the functionalization of the precursor polyperoxides. Water soluble polyperoxides were also prepared, and the LCST behavior and the application to a drug carrier in the drug delivery system were investigated. In order to design various types of degradable polymers and gels we developed a method for the introduction of dienyl groups into the precursor polymers. The resulting dienyl-functionalized polymers were used for the degradable gels. The degradable branched copolymers showed a microphase-separated structure, which changed owing to the degradation of the polyperoxide segments. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

The bus transit system : ITS underutilized potential

DOT National Transportation Integrated Search

1994-05-01

The bus system represents the most widely used transit mode. Upgraded bus services, primarily those which have partially or fully separated rights-of-way, represent a very cost-effective method to improve the balance between automobile and transit. M...

Ultrafast Dynamics in Vanadium Dioxide: Separating Spatially Segregated Mixed Phase Dynamics in the Time-domain

NASA Astrophysics Data System (ADS)

Hilton, David

2011-10-01

In correlated electronic systems, observed electronic and structural behavior results from the complex interplay between multiple, sometimes competing degrees-of- freedom. One such material used to study insulator-to-metal transitions is vanadium dioxide, which undergoes a phase transition from a monoclinic-insulating phase to a rutile-metallic phase when the sample is heated to 340 K. The major open question with this material is the relative influence of this structural phase transition (Peirels transition) and the effects of electronic correlations (Mott transition) on the observed insulator-to-metal transition. Answers to these major questions are complicated by vanadium dioxide's sensitivity to perturbations in the chemical structure in VO2. For example, related VxOy oxides with nearly a 2:1 ratio do not demonstrate the insulator-to- metal transition, while recent work has demonstrated that W:VO2 has demonstrated a tunable transition temperature controllable with tungsten doping. All of these preexisting results suggest that the observed electronic properties are exquisitely sensitive to the sample disorder. Using ultrafast spectroscopic techniques, it is now possible to impulsively excite this transition and investigate the photoinduced counterpart to this thermal phase transition in a strongly nonequilibrium regime. I will discuss our recent results studying the terahertz-frequency conductivity dynamics of this photoinduced phase transition in the poorly understood near threshold temperature range. We find a dramatic softening of the transition near the critical temperature, which results primarily from the mixed phase coexistence near the transition temperature. To directly study this mixed phase behavior, we directly study the nucleation and growth rates of the metallic phase in the parent insulator using non-degenerate optical pump-probe spectroscopy. These experiments measure, in the time- domain, the coexistent phase separation in VO2 (spatially separated insulator and metal islands) and, more importantly, their dynamic evolution in response to optical excitation.

Equilibrium polymerization models of re-entrant self-assembly

NASA Astrophysics Data System (ADS)

Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

2009-04-01

As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

Ordering-separation phase transitions in a Co3V alloy

NASA Astrophysics Data System (ADS)

Ustinovshchikov, Yu. I.

2017-01-01

The microstructure of the Co3V alloy formed by heat treatment at various temperatures is studied by transmission electron microscopy. Two ordering-separation phase transitions are revealed at temperatures of 400-450 and 800°C. At the high-temperature phase separation, the microstructure consists of bcc vanadium particles and an fcc solid solution; at the low-temperature phase separation, the microstructure is cellular. In the ordering range, the microstructure consists of chemical compound Co3V particles chaotically arranged in the solid solution. The structure of the Co3V alloy is shown not to correspond to the structures indicated in the Co-V phase diagram at any temperatures.

Superfluid Densities in Superconducting/Ferromagnetic (Nb/NiV/Nb) Heterostructures

NASA Astrophysics Data System (ADS)

Hinton, Michael; Peters, Brian; Hauser, Adam; Meyer, Julia; Yang, Fengyuan; Lemberger, Thomas

2011-03-01

Superfluid density measurements allow us to probe the superconducting structure of thin films below Tc with remarkable detail. They yield information not only of the inherent robustness of the superconducting state, but also about the homogeneity of the sample and possible ``hidden'' transitions at temperatures lower than the initial Tc . For this reason multiple transitions in superconducting heterostructures are revealed to us. We use superfluid density measurements on Nb/ Ni 0.95 V0.05 /Nb trilayers to study the interplay between two superconducting films separated by the destructive proximity effects of a ferromagnet. We show there are trilayers with strong coupling, which produces a single transition, that become decoupled to the point of separation into two transitions as the ferromagnetic layer thickness increases. We discuss the difficulties in observing the second transition in σ1 , while obvious in λ-2 .

45 CFR 618.230 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 45 Public Welfare 3 2010-10-01 2010-10-01 false Transition plans. 618.230 Section 618.230 Public... Coverage § 618.230 Transition plans. (a) Submission of plans. An institution to which § 618.225 applies and... plan applicable to all such units, or a separate transition plan applicable to each such unit. (b...

34 CFR 106.17 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 34 Education 1 2010-07-01 2010-07-01 false Transition plans. 106.17 Section 106.17 Education... Coverage § 106.17 Transition plans. (a) Submission of plans. An institution to which § 106.16 applies and... plan applicable to all such units, or a separate transition plan applicable to each such unit. (b...

Numerical investigation of hypersonic flat-plate boundary layer transition mechanism induced by different roughness shapes

NASA Astrophysics Data System (ADS)

Zhou, Yunlong; Zhao, Yunfei; Xu, Dan; Chai, Zhenxia; Liu, Wei

2016-10-01

The roughness-induced laminar-turbulent boundary layer transition is significant for high-speed aerospace applications. The transition mechanism is closely related to the roughness shape. In this paper, high-order numerical method is used to investigate the effect of roughness shape on the flat-plate laminar-to-turbulent boundary layer transition. Computations are performed in both the supersonic and hypersonic regimes (free-stream Mach number from 3.37 up to 6.63) for the square, cylinder, diamond and hemisphere roughness elements. It is observed that the square and diamond roughness elements are more effective in inducing transition compared with the cylinder and hemisphere ones. The square roughness element has the longest separated region in which strong unsteadiness exists and the absolute instability is formed, thus resulting in the earliest transition. The diamond roughness element has a maximum width of the separated region leading to the widest turbulent wake region far downstream. Furthermore, transition location moves backward as the Mach number increases, which indicates that the compressibility significantly suppresses the roughness-induced boundary layer transition.

BKT phase transition in a 2D system with long-range dipole-dipole interaction

NASA Astrophysics Data System (ADS)

Fedichev, P. O.; Men'shikov, L. I.

2012-01-01

We consider phase transitions in 2D XY-like systems with long-range dipole-dipole interactions and demonstrate that BKT-type phase transition always occurs separating the ordered (ferroelectric) and the disordered (paraelectric) phases. The low-temperature phase corresponds to a thermal state with bound vortex-antivortex pairs characterized by linear attraction at large distances. Using the Maier-Schwabl topological charge model, we show that bound vortex pairs polarize and screen the vortex-antivortex interaction, leaving only the logarithmic attraction at sufficiently large separations between the vortices. At higher temperatures the pairs dissociate and the phase transition similar to BKT occurs, though at a larger temperature than in a system without the dipole-dipole interaction.

Optical absorption by indirect excitons in a transition metal dichalcogenide/hexagonal boron nitride heterostructure

NASA Astrophysics Data System (ADS)

Brunetti, Matthew N.; Berman, Oleg L.; Kezerashvili, Roman Ya

2018-06-01

We study optical transitions in spatially indirect excitons in transition metal dichalcogenide (TMDC) heterostructures separated by an integer number of hexagonal boron nitride (h-BN) monolayers. By solving the Schrödinger equation with the Keldysh potential for a spatially indirect exciton, we obtain eigenfunctions and eigenenergies for the ground and excited states and study their dependence on the interlayer separation, controlled by varying the number of h-BN monolayers. The oscillator strength, optical absorption coefficient, and optical absorption factor, the fraction of incoming photons absorbed in the TMDC/h-BN/TMDC heterostructure, are evaluated and studied as a function of the interlayer separation. Using input parameters from the existing literature which give the largest and the smallest spatially indirect exciton binding energy, we provide upper and lower bounds on all quantities presented.

Separation of transition metals on a poly-iminodiacetic acid grafted polymeric resin column with post-column reaction detection utilising a paired emitter-detector diode system.

PubMed

Barron, Leon; O'Toole, Martina; Diamond, Dermot; Nesterenko, Pavel N; Paull, Brett

2008-12-05

The selectivity, retention and separation of transition metals on a short (2 mm x 50 mm) column packed with a poly-iminodiacetic acid functionalised polymer 10 microm resin (Dionex ProPac IMAC-10) are presented. This stationary phase, typically used for the separation of proteins, is composed of long chain poly-iminodiacetic acid groups grafted to a hydrophilic layer surrounding a 10 microm polymeric bead. Through the use of a combination of a multi-step pH and picolinic acid gradient, the separation of magnesium, iron, cobalt, cadmium, zinc, lead and copper was possible, followed by post-column reaction with 4-(2-pyridylazo) resorcinol (PAR) and absorbance detection at 510 nm using a novel and inexpensive optical detector, comprised of two light emitting diodes with one acting as a light source and the other as a detector. Column efficiency for selective transition metals was in excess of N=10,000, with the baseline separation of seven metal cations in <3 min possible under optimised conditions. Detection limits of between 5 and 81 microg/L were possible based upon a 50 microL injection volume.

Supporting drivers in forming correct expectations about transitions between rural road categories.

PubMed

Stelling-Konczak, Agnieszka; Aarts, Letty; Duivenvoorden, Kirsten; Goldenbeld, Charles

2011-01-01

In order to support drivers in forming the right expectations on the road, road categories are being made recognisable and predictable in the Netherlands. The present study investigated which of the selected road layouts can make rural road categories most recognisable for road users, especially in transitions from one road category to another. A second objective was to study whether explicit information could contribute to a better recognisability of transitions. The experiment was performed with a series of photographs showing sections of two road categories with an intersection in between. The road layout of road categories varied in markings and separation of driving direction (within-subjects factor). Informed and non-informed participants (between-subjects factor) had to indicate their expectations regarding speed limit and access restriction of each road section, before and after a transition. The results show that for transitions between distributor and through roads, the physicality of separation of driving direction is a better distinctive characteristic than the currently used edge marking. The green centre marking on through roads also enhances recognisability, but only with additional information. As far as transitions between distributor and access roads are concerned, the results demonstrate that this type of transitions is better recognised when no markings on access roads are present. Physical separation of driving directions on distributor roads also improves recognisability, although this layout is associated with higher speed limits. Providing explicit information has in general a positive effect on the reconisability of transitions. Implications are discussed in the light of potential safety effects. Copyright © 2010 Elsevier Ltd. All rights reserved.

Pressures Around an Inclined Ogive Cylinder with Laminar, Transitional, or Turbulent Separation

NASA Technical Reports Server (NTRS)

Lamont, P. J.

1982-01-01

This paper reports results From comprehensive pressure tests on an ogive cylinder in the low-turbulence 12-ft pressure wind tunnel at Ames Research Center. The results consist of detailed pressure distributions over a wide range of Reynolds numbers (0.2 x 10(exp 6) to 4.0 x 10(exp 6)) and angles of attack (20 to 90 deg). Most important, the tests encompassed a complete coverage of different roll orientations. This variation of roll orientation is shown to be essential in order to fully define all the possible flow conditions. When the various roll-angle results are combined, it is possible to interpret correctly the effects of changing angle of attack or Reynolds number. Two basic mechanisms for producing asymmetric flow are identified. One mechanism operates in both the laminar and the fully turbulent separation regimes; this mechanism Is the one qualitatively described by the impulsive flow analogy. The other mechanism occurs only in the transitional separation regime. This asymmetric flow has the same form as that found in the two-dimensional cross flow on a circular cylinder in the transitional flow regime. Finally, these results make it possible to draw up critical Reynolds number boundaries between the laminar, transitional, and fully turbulent separation regimes throughout the angle-of-attack range from 20 to 90 deg.

Hierarchical Bayesian calibration of tidal orbit decay rates among hot Jupiters

NASA Astrophysics Data System (ADS)

Collier Cameron, Andrew; Jardine, Moira

2018-05-01

Transiting hot Jupiters occupy a wedge-shaped region in the mass ratio-orbital separation diagram. Its upper boundary is eroded by tidal spiral-in of massive, close-in planets and is sensitive to the stellar tidal dissipation parameter Q_s^'. We develop a simple generative model of the orbital separation distribution of the known population of transiting hot Jupiters, subject to tidal orbital decay, XUV-driven evaporation and observational selection bias. From the joint likelihood of the observed orbital separations of hot Jupiters discovered in ground-based wide-field transit surveys, measured with respect to the hyperparameters of the underlying population model, we recover narrow posterior probability distributions for Q_s^' in two different tidal forcing frequency regimes. We validate the method using mock samples of transiting planets with known tidal parameters. We find that Q_s^' and its temperature dependence are retrieved reliably over five orders of magnitude in Q_s^'. A large sample of hot Jupiters from small-aperture ground-based surveys yields log _{10} Q_s^' }=(8.26± 0.14) for 223 systems in the equilibrium-tide regime. We detect no significant dependence of Q_s^' on stellar effective temperature. A further 19 systems in the dynamical-tide regime yield log _{10} Q_s^' }=7.3± 0.4, indicating stronger coupling. Detection probabilities for transiting planets at a given orbital separation scale inversely with the increase in their tidal migration rates since birth. The resulting bias towards younger systems explains why the surface gravities of hot Jupiters correlate with their host stars' chromospheric emission fluxes. We predict departures from a linear transit-timing ephemeris of less than 4 s for WASP-18 over a 20-yr baseline.

Prediction and Analysis of the Nonsteady Transition and Separation Processes on an Oscillating Wind Turbine Airfoil using the \\gamma-Re_\\theta Transition Model.

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

Nandi, Taraj; Brasseur, James; Vijayakumar, Ganesh

2016-01-04

This study is aimed at gaining insight into the nonsteady transitional boundary layer dynamics of wind turbine blades and the predictive capabilities of URANS based transition and turbulence models for similar physics through the analysis of a controlled flow with similar nonsteady parameters.

Minnowbrook III: 2000 Workshop on Boundary Layer Transition and Unsteady Aspects of Turbomachinery Flows

NASA Technical Reports Server (NTRS)

LaGraff, John E. (Editor); Ashpis, David E. (Editor)

2002-01-01

This volume and its accompanying CD-ROM contain materials presented at the Minnowbrook III-2000 Workshop on Boundary Layer Transition and Unsteady Aspects of Turbomachinery Flows held at the Syracuse University Minnowbrook Conference Center, Blue Mountain Lake, New York, August 20-23, 2000. Workshop organizers were John E. LaGraff (Syracuse University), Terry V Jones (Oxford University), and J. Paul Gostelow (University of Leicester). The workshop followed the theme, venue, and informal format of two earlier workshops: Minnowbrook I (1993) and Minnowbrook II (1997). The workshop was focused on physical understanding the late stage (final breakdown) boundary layer transition, separation, and effects of unsteady wakes with the specific goal of contributing to engineering application of improving design codes for turbomachinery. The workshop participants included academic researchers from the USA and abroad, and representatives from the gas-turbine industry and government laboratories. The physical mechanisms discussed included turbulence disturbance environment in turbomachinery, flow instabilities, bypass and natural transition, turbulent spots and calmed regions, wake interactions with attached and separated boundary layers, turbulence and transition modeling and CFD, and DNS. This volume contains abstracts and copies of the viewgraphs presented, organized according to the workshop sessions. The viewgraphs are included on the CD-ROM only. The workshop summary and the plenary-discussion transcripts clearly highlight the need for continued vigorous research in the technologically important area of transition, separated and unsteady flows in turbomachines.

ALESEP. Part 2: A computer program for the analysis of leading edge separation bubbles on infinite swept wings

NASA Technical Reports Server (NTRS)

Davis, R. L.

1986-01-01

A program called ALESEP is presented for the analysis of the inviscid-viscous interaction which occurs due to the presence of a closed laminar-transitional separation bubble on an airfoil or infinite swept wing. The ALESEP code provides an iterative solution of the boundary layer equations expressed in an inverse formulation coupled to a Cauchy integral representation of the inviscid flow. This interaction analysis is treated as a local perturbation to a known solution obtained from a global airfoil analysis; hence, part of the required input to the ALESEP code are the reference displacement thickness and tangential velocity distributions. Special windward differencing may be used in the reversed flow regions of the separation bubble to accurately account for the flow direction in the discretization of the streamwise convection of momentum. The ALESEP code contains a forced transition model based on a streamwise intermittency function, a natural transition model based on a solution of the integral form of the turbulent kinetic energy equation, and an empirical natural transition model.

On the Unsteadiness of a Transitional Shock Wave-Boundary Layer Interaction Using Fast-Response Pressure-Sensitive Paint

NASA Astrophysics Data System (ADS)

Lash, E. Lara; Schmisseur, John

2017-11-01

Pressure-sensitive paint has been used to evaluate the unsteady dynamics of transitional and turbulent shock wave-boundary layer interactions generated by a vertical cylinder on a flat plate in a Mach 2 freestream. The resulting shock structure consists of an inviscid bow shock that bifurcates into a separation shock and trailing shock. The primary features of interest are the separation shock and an upstream influence shock that is intermittently present in transitional boundary layer interactions, but not observed in turbulent interactions. The power spectral densities, frequency peaks, and normalized wall pressures are analyzed as the incoming boundary layer state changes from transitional to fully turbulent, comparing both centerline and outboard regions of the interaction. The present study compares the scales and frequencies of the dynamics of the separation shock structure in different boundary layer regimes. Synchronized high-speed Schlieren imaging provides quantitative statistical analyses as well as qualitative comparisons to the fast-response pressure sensitive paint measurements. Materials based on research supported by the U.S. Office of Naval Research under Award Number N00014-15-1-2269.

Numerical simulation of transitional flow on a wind turbine airfoil with RANS-based transition model

NASA Astrophysics Data System (ADS)

Zhang, Ye; Sun, Zhengzhong; van Zuijlen, Alexander; van Bussel, Gerard

2017-09-01

This paper presents a numerical investigation of transitional flow on the wind turbine airfoil DU91-W2-250 with chord-based Reynolds number Rec = 1.0 × 106. The Reynolds-averaged Navier-Stokes based transition model using laminar kinetic energy concept, namely the k - kL - ω model, is employed to resolve the boundary layer transition. Some ambiguities for this model are discussed and it is further implemented into OpenFOAM-2.1.1. The k - kL - ω model is first validated through the chosen wind turbine airfoil at the angle of attack (AoA) of 6.24° against wind tunnel measurement, where lift and drag coefficients, surface pressure distribution and transition location are compared. In order to reveal the transitional flow on the airfoil, the mean boundary layer profiles in three zones, namely the laminar, transitional and fully turbulent regimes, are investigated. Observation of flow at the transition location identifies the laminar separation bubble. The AoA effect on boundary layer transition over wind turbine airfoil is also studied. Increasing the AoA from -3° to 10°, the laminar separation bubble moves upstream and reduces in size, which is in close agreement with wind tunnel measurement.

Outcome Evaluation of the Army Career and Alumni Program’s Job Assistance Centers.

DTIC Science & Technology

1995-10-01

The Army Career and Alumni Program offers transition services to servicemembers and their families as well as to Army civilian employees who are...separating from the service. This report evaluates the functions of the Job Assistance Centers (JAC) at which these services are provided. Approximately...3,000 ex-servicemembers (Army, Navy, Marines, and Air Force), spouses, and separated civilian employees who transitioned between 1 October 1992 and 30

Formation of structural steady states in lamellar/sponge phase-separating fluids under shear flow

NASA Astrophysics Data System (ADS)

Panizza, P.; Courbin, L.; Cristobal, G.; Rouch, J.; Narayanan, T.

2003-05-01

We investigate the effect of shear flow on a lamellar-sponge phase-separating fluid when subjected to shear flow. We show the existence of two different steady states (droplets and ribbons structures) whose nature does not depend on the way to reach the two-phase unstable region of the phase diagram (temperature quench or stirring). The transition between ribbons and droplets is shear thickening and its nature strongly depends on what dynamical variable is imposed. If the stress is fixed, flow visualization shows the existence of shear bands at the transition, characteristic of coexistence in the cell between ribbons and droplets. In this shear-banding region, the viscosity oscillates. When the shear rate is fixed, no shear bands are observed. Instead, the transition exhibits a hysteretic behavior leading to a structural bi-stability of the phase-separating fluid under flow.

Selective Hydrogen Isotope Separation via Breathing Transition in MIL-53(Al).

PubMed

Kim, Jin Yeong; Zhang, Linda; Balderas-Xicohténcatl, Rafael; Park, Jaewoo; Hirscher, Michael; Moon, Hoi Ri; Oh, Hyunchul

2017-12-13

Breathing of MIL-53(Al), a flexible metal-organic framework (MOF), leads to dynamic changes as narrow pore (np) transitions to large pore (lp). During the flexible and reversible transition, the pore apertures are continuously adjusted, thus providing the tremendous opportunity to separate mixtures of similar-sized and similar-shaped molecules that require precise pore tuning. Herein, for the first time, we report a strategy for effectively separating hydrogen isotopes through the dynamic pore change during the breathing of MIL-53(Al), a representative of flexible MOFs. The experiment shows that the selectivity for D 2 over H 2 is strongly related to the state of the pore structure of MIL-53(Al). The highest selectivity (S D 2 /H 2 = 13.6 at 40 K) was obtained by optimizing the exposure temperature, pressure, and time to systematically tune the pore state of MIL-53(Al).

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

NASA Astrophysics Data System (ADS)

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; Kreyssig, Andreas; Ran, S.; Bud'ko, Sergey L.; Canfield, Paul C.; Mompean, Federico J.; García-Hernández, Mar; Munuera, Carmen; Guillamón, Isabel; Suderow, Hermann

2018-01-01

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co-substituted CaFe2As2 . We use atomic force, magnetic force, and scanning tunneling microscopy to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micrometers long and about 30 nm wide; have the same Tc as unstrained samples; and hold vortices in a magnetic field. Thus, biaxial strain produces a phase-separated state, where each phase is equivalent to what is found on either side of the first-order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of the order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first-order quantum phase transitions lead to nanometric-size phase separation under the influence of strain.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe 2 As 2 close to a first-order phase transition

DOE PAGES

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; ...

2018-01-09

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

A Child's Use of Transitional Objects in Art Therapy to Cope with Divorce

ERIC Educational Resources Information Center

McCullough, Courtney

2009-01-01

In this article, the author examines the use of transitional objects in a case study of a 12-year-old boy, documenting the role of art therapy in helping the boy cope with the trauma of his parents' recent separation and divorce. Transitional objects emerged spontaneously as the boy integrated the transition that the divorce of his parents…

Visualization of the separation and subsequent transition near the leading edge of airfoils

NASA Technical Reports Server (NTRS)

Arena, A. V.; Mueller, T. J.

1978-01-01

A visual study was performed using the low speed smoke wind tunnels with the objective of obtaining a better understanding of the structure of leading edge separation bubbles on airfoils. The location of separation, transition and reattachment for a cylindrical nose constant-thickness airfoil model were obtained from smoke photographs and surface oil flow techniques. These data, together with static pressure distributions along the leading edge and upper surface of the model, produced the influence of Reynolds number, angle of attack, and trailing edge flap angle on the size and characteristics of the bubble. Additional visual insight into the unsteady nature of the separation bubble was provided by high speed 16 mm movies. The 8 mm color movies taken of the surface oil flow supported the findings of the high speed movies and clearly showed the formation of a scalloped spanwise separation line at the higher Reynolds number.

19 CFR 123.22 - In-transit manifest.

Code of Federal Regulations, 2011 CFR

2011-04-01

... separate in-transit manifest is not required. (b) Additional copies. In the following cases additional... train sheet shall also be presented. (4) In all other cases where no in-transit manifest form is... enter and reenter Canada in a continuing movement en route to a final destination in the United States...

19 CFR 123.22 - In-transit manifest.

Code of Federal Regulations, 2014 CFR

2014-04-01

... separate in-transit manifest is not required. (b) Additional copies. In the following cases additional... train sheet shall also be presented. (4) In all other cases where no in-transit manifest form is... enter and reenter Canada in a continuing movement en route to a final destination in the United States...

19 CFR 123.22 - In-transit manifest.

Code of Federal Regulations, 2013 CFR

2013-04-01

... separate in-transit manifest is not required. (b) Additional copies. In the following cases additional... train sheet shall also be presented. (4) In all other cases where no in-transit manifest form is... enter and reenter Canada in a continuing movement en route to a final destination in the United States...

Live cell plasma membranes do not exhibit a miscibility phase transition over a wide range of temperatures.

PubMed

Lee, Il-Hyung; Saha, Suvrajit; Polley, Anirban; Huang, Hector; Mayor, Satyajit; Rao, Madan; Groves, Jay T

2015-03-26

Lipid/cholesterol mixtures derived from cell membranes as well as their synthetic reconstitutions exhibit well-defined miscibility phase transitions and critical phenomena near physiological temperatures. This suggests that lipid/cholesterol-mediated phase separation plays a role in the organization of live cell membranes. However, macroscopic lipid-phase separation is not generally observed in cell membranes, and the degree to which properties of isolated lipid mixtures are preserved in the cell membrane remain unknown. A fundamental property of phase transitions is that the variation of tagged particle diffusion with temperature exhibits an abrupt change as the system passes through the transition, even when the two phases are distributed in a nanometer-scale emulsion. We support this using a variety of Monte Carlo and atomistic simulations on model lipid membrane systems. However, temperature-dependent fluorescence correlation spectroscopy of labeled lipids and membrane-anchored proteins in live cell membranes shows a consistently smooth increase in the diffusion coefficient as a function of temperature. We find no evidence of a discrete miscibility phase transition throughout a wide range of temperatures: 14-37 °C. This contrasts the behavior of giant plasma membrane vesicles (GPMVs) blebbed from the same cells, which do exhibit phase transitions and macroscopic phase separation. Fluorescence lifetime analysis of a DiI probe in both cases reveals a significant environmental difference between the live cell and the GPMV. Taken together, these data suggest the live cell membrane may avoid the miscibility phase transition inherent to its lipid constituents by actively regulating physical parameters, such as tension, in the membrane.

Cation separation and preconcentration using columns containing cyclen and cyclen-resorcinarene derivatives.

PubMed

Li, Na; English, Christopher; Eaton, Ammon; Gillespie, Austin; Ence, T C; Christensen, Taylor J; Sego, Adam; Harrison, Roger G; Lamb, John D

2012-07-06

The selectivity and separation of transition metal ions on two columns packed with cyclen-based macrocycles adsorbed onto 55% cross-linked styrene-divinylbenzene resin are presented. The N-cyclen and cyclen-resorcinarene stationary phases were made by adsorbing hydrophobically substituted N-cyclen or a cyclen-resorcinarene derivative (cyclenbowl) on the resin, respectively. The stability constants of cyclen with transition metal ions demonstrate that cyclen has selectivity for Cu²⁺ over other transition metal ions. Mn²⁺, Co²⁺, Ni²⁺, Cd²⁺, and Zn²⁺ ions were separated from Cu²⁺ using HNO₃ eluent with the cyclenbowl column. The preconcentration of Cu²⁺ in parts per billion level from a high concentration matrix of Mn²⁺, Co²⁺, Ni²⁺, Cd²⁺, and Zn²⁺ ions was achieved in the cyclenbowl column using a nitric acid eluent gradient. Recovery of Cu²⁺ at >98% was obtained based on direct interaction of metal ion and cyclen. Although Mn²⁺, Co²⁺, Ni²⁺, Cd²⁺, and Zn²⁺ were not separated by HNO₃ eluent, addition of oxalic acid yielded a very good separation. A retention mechanism is proposed for the latter system in which the protonated cyclen units attract negatively charged HC₂O₄⁻ ions that cooperate with cyclen sites in retaining transition metal ions. Copyright © 2012 Elsevier B.V. All rights reserved.

STICK-SLIP-SEPARATION Analysis and Non-Linear Stiffness and Damping Characterization of Friction Contacts Having Variable Normal Load

NASA Astrophysics Data System (ADS)

Yang, B. D.; Chu, M. L.; Menq, C. H.

1998-03-01

Mechanical systems in which moving components are mutually constrained through contacts often lead to complex contact kinematics involving tangential and normal relative motions. A friction contact model is proposed to characterize this type of contact kinematics that imposes both friction non-linearity and intermittent separation non-linearity on the system. The stick-slip friction phenomenon is analyzed by establishing analytical criteria that predict the transition between stick, slip, and separation of the interface. The established analytical transition criteria are particularly important to the proposed friction contact model for the transition conditions of the contact kinematics are complicated by the effect of normal load variation and possible interface separation. With these transition criteria, the induced friction force on the contact plane and the variable normal load perpendicular to the contact plane, can be predicted for any given cyclic relative motions at the contact interface and hysteresis loops can be produced so as to characterize the equivalent damping and stiffness of the friction contact. These-non-linear damping and stiffness methods along with the harmonic balance method are then used to predict the resonant response of a frictionally constrained two-degree-of-freedom oscillator. The predicted results are compared with those of the time integration method and the damping effect, the resonant frequency shift, and the jump phenomenon are examined.

Thermodynamics and structural transition of binary atomic Bose-Fermi mixtures in box or harmonic potentials: A path-integral study

NASA Astrophysics Data System (ADS)

Kim, Tom; Chien, Chih-Chun

2018-03-01

Experimental realizations of a variety of atomic binary Bose-Fermi mixtures have brought opportunities for studying composite quantum systems with different spin statistics. The binary atomic mixtures can exhibit a structural transition from a mixture into phase separation as the boson-fermion interaction increases. By using a path-integral formalism to evaluate the grand partition function and the thermodynamic grand potential, we obtain the effective potential of binary Bose-Fermi mixtures. Thermodynamic quantities in a broad range of temperatures and interactions are also derived. The structural transition can be identified as a loop of the effective potential curve, and the volume fraction of phase separation can be determined by the lever rule. For 6Li-7Li and 6Li-41K mixtures, we present the phase diagrams of the mixtures in a box potential at zero and finite temperatures. Due to the flexible densities of atomic gases, the construction of phase separation is more complicated when compared to conventional liquid or solid mixtures where the individual densities are fixed. For harmonically trapped mixtures, we use the local density approximation to map out the finite-temperature density profiles and present typical trap structures, including the mixture, partially separated phases, and fully separated phases.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Separation: Supporting Children in Their Preschool Transitions. Revised Edition

ERIC Educational Resources Information Center

Jervis, Kathe; Polland, Barbara K.

2007-01-01

This book, updated since initial publication in 1989, offers explanations, practical tips, and encouragement for teachers and families of preschool children facing the excitement--and stress--of separation. Topics discussed include ambivalence about separation and attachment, the comfort of routines, understanding the child perspective, supporting…

Optical imaging beyond the diffraction limit by SNEM: effects of AFM tip modifications with thiol monolayers on imaging quality.

PubMed

Cumurcu, Aysegul; Diaz, Jordi; Lindsay, Ian D; de Beer, Sissi; Duvigneau, Joost; Schön, Peter; Julius Vancso, G

2015-03-01

Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Comb and Centipede Multigraft Copolymers P nBA- g-PS with High Molecular Weight Using Miniemulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Lu, Xinyi; ...

2014-10-23

For this study, comb and centipede multigraft copolymers, poly(n-butyl acrylate)-g-polystyrene (PnBA-g-PS) with PnBA backbones and PS side chains, were synthesized via high-vacuum anionic polymerization and miniemulsion polymerization. Single-tailed and double-tailed PS macromonomers were synthesized by anionic polymerization and Steglich esterification. Subsequently, the copolymerization of each macromonomer and nBA was carried out in miniemulsion, and multigraft copolymers were obtained. The latex particles of multigraft copolymers were characterized using dynamic light scattering. The molecular weights of macromonomers and multigraft copolymers were analyzed by size exclusion chromatography. Moreover, the molecular weights and structures of macromonomers were investigated by matrix-assisted laser desorption/ionization time-of-flight massmore » spectrometry and 1H nuclear magnetic resonance spectroscopy. The weight contents of PS in comb and centipede multigraft copolymers were calculated by 1H nuclear magnetic resonance spectroscopy. The thermal properties of multigraft copolymers were characterized by thermogravimetric analysis and differential scanning calorimetry. The microphase separation of multigraft copolymers was observed by atomic force microscopy and transmission electronic microscopy. Rheological measurements showed that comb and centipede multigraft copolymers have elastic properties when the weight content of PS side chains is 26–32 wt %. Centipede multigraft copolymers possess better elastic properties than comb multigraft copolymers with the similar weight content of PS. In conclusion, these findings are similar to previous results on poly(isoprene-g-polystyrene) comb and centipede copolymers made by anionic polymerization.« less

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

Goodwin, Andrew; Wang, Weiyu; Kang, Nam -Goo

We present in this paper the synthesis of poly(n-butyl acrylate)-g-poly(methyl methacrylate) (PnBA-g-PMMA) multigraft copolymers via a grafting-through (macromonomer) approach. The synthesis was performed using two controlled polymerization techniques. The PMMA macromonomer was obtained by high-vacuum anionic polymerization followed by the copolymerization of n-butyl acrylate and PMMA macromonomer using reversible addition–fragmentation chain transfer (RAFT) polymerization to yield the desired all-acrylic multigraft structures. The PnBA-g-PMMA multigraft structures exhibit randomly spaced branch points with various PMMA contents, ranging from 15 to 40 vol %, allowing an investigation into how physical properties vary with differences in the number of branch points and molecular weightmore » of grafted side chains. The determination of molecular weight and polydispersity indices of both the PMMA macromonomer and the graft copolymers was carried out using size exclusion chromatography with triple detection, and the structural characteristics of both the macromonomer and PnBA-g-PMMA graft materials were characterized by 1H and 13C NMR. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was employed for monitoring the macromonomer synthesis. Thermal characteristics of the materials were analyzed using differential scanning calorimetry and thermogravimetric analysis. The mechanical performance of the graft materials was characterized by rheology and dynamic mechanical analysis, revealing that samples with PMMA content of 25–40 vol % exhibit superior elastomeric properties as compared to materials containing short PMMA side chains or <25 vol % PMMA. In conclusion, atomic force microscopy showed a varying degree of microphase separation between the glassy and rubbery components that is strongly dependent on PMMA side chain molecular weight.« less

Self-consistent field theory and numerical scheme for calculating the phase diagram of wormlike diblock copolymers

NASA Astrophysics Data System (ADS)

Jiang, Ying; Chen, Jeff Z. Y.

2013-10-01

This paper concerns establishing a theoretical basis and numerical scheme for studying the phase behavior of AB diblock copolymers made of wormlike chains. The general idea of a self-consistent field theory is the combination of the mean-field approach together with a statistical weight that describes the configurational properties of a polymer chain. In recent years, this approach has been extensively used for structural prediction of block copolymers, based on the Gaussian-model description of a polymer chain. The wormlike-chain model has played an important role in the description of polymer systems, covering the semiflexible-to-rod crossover of the polymer properties and the highly stretching regime, which the Gaussian-chain model has difficulties to describe. Although the idea of developing a self-consistent field theory for wormlike chains could be traced back to early development in polymer physics, the solution of such a theory has been limited due to technical difficulties. In particular, a challenge has been to develop a numerical algorithm enabling the calculation of the phase diagram containing three-dimensional structures for wormlike AB diblock copolymers. This paper describes a computational algorithm that combines a number of numerical tricks, which can be used for such a calculation. A phase diagram covering major parameter areas was constructed for the wormlike-chain system and reported by us, where the ratio between the total length and the persistence length of a constituent polymer is suggested as another tuning parameter for the microphase-separated structures; all detailed technical issues are carefully addressed in the current paper.

Transition control of Mach to regular reflection induced interaction using an array of micro ramp vane-type vortex generators

NASA Astrophysics Data System (ADS)

Verma, Shashi B.; Chidambaranathan, Manisankar

2015-10-01

An experimental investigation has been conducted to favorably control/modify a Mach reflection induced interaction in a Mach 2.05 flow on a flat plate using an array of single row mechanical micro vane-type vortex generators (VGs). The objective was to study the variation in (i) control device configuration (trapezoidal and the split-trapezoidal or ramp vane-type), (ii) control device height (h/δ = 0.3, 0.5), and (iii) control location (X/δ = 9, 15 upstream of the interaction) in controlling the overall interaction. The primary aim was to investigate a control location and VG configuration which is able to effectively initiate a transition from Mach reflection to regular reflection with minimum changes to the separation characteristics for no control. While the trapezoidal configuration is seen to move the separation location upstream only slightly, the split-trapezoidal configurations result in a considerable upstream movement that is associated with significant reduction in separation shock strength. The latter flow modification causes the Mach stem to completely disappear resulting in a transition from Mach to regular reflection. The control location of X/δ = 15 seems to be most effective for all control device configurations tested. It is further observed that whilst the effectiveness of the split-trapezoidal configuration of h/δ = 0.3 in controlling the transition improves with increasing X/δ, increasing its height to h/δ = 0.5 not only controls the transition process but is also able to control the extent of separation. All the control devices, however, are seen to increase the flow unsteadiness in the intermittent region of separation for both control locations. From this perspective, increasing the height of the control device seems favorable for the closer control location as it not only completely modifies the Mach reflection but also keeps the peak rms value similar to the baseline case.

Youth Transition from Adolescence to the World of Work.

ERIC Educational Resources Information Center

Mangum, Garth L.

Despite the fact that American society persistently separates home from workplace and extends adolescence, most American youth make the school-to-work transition with a minimum of pain and reasonable success. A substantial minority do not, however, and there is need to improve the transition process especially for those who have been economically…

Supporting Students in Military Families during Times of Transition: A Call for Awareness and Action

ERIC Educational Resources Information Center

Cole, Rebekah F.

2017-01-01

Throughout their time in school, students in military families face many challenging periods of transition, which include deployments, relocations, and the family's separation from the military. During these transitions, students in military families may be especially susceptible to social, emotional, and academic challenges both in their home…

41 CFR 101-4.230 - Transition plans.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 41 Public Contracts and Property Management 2 2010-07-01 2010-07-01 true Transition plans. 101-4... plans. (a) Submission of plans. An institution to which § 101-4.225 applies and that is composed of more than one administratively separate unit may submit either a single transition plan applicable to all...

Transition to Old Age (Transition to Retirement).

ERIC Educational Resources Information Center

Bergman, Simon

Several conceptualizations and definitions of retirement have been proposed. One of them--the three-stage transition process--can be illustrated from studies in Israel: (1) leaving the old role; (2) going through the act of formal separation; and (3) adjusting to the new situation and role. Today's higher rate of survival into later years means…

Non-Linear Relationship between Economic Growth and CO2 Emissions in China: An Empirical Study Based on Panel Smooth Transition Regression Models

PubMed Central

Wang, Zheng-Xin; Hao, Peng; Yao, Pei-Yi

2017-01-01

The non-linear relationship between provincial economic growth and carbon emissions is investigated by using panel smooth transition regression (PSTR) models. The research indicates that, on the condition of separately taking Gross Domestic Product per capita (GDPpc), energy structure (Es), and urbanisation level (Ul) as transition variables, three models all reject the null hypothesis of a linear relationship, i.e., a non-linear relationship exists. The results show that the three models all contain only one transition function but different numbers of location parameters. The model taking GDPpc as the transition variable has two location parameters, while the other two models separately considering Es and Ul as the transition variables both contain one location parameter. The three models applied in the study all favourably describe the non-linear relationship between economic growth and CO2 emissions in China. It also can be seen that the conversion rate of the influence of Ul on per capita CO2 emissions is significantly higher than those of GDPpc and Es on per capita CO2 emissions. PMID:29236083

Non-Linear Relationship between Economic Growth and CO₂ Emissions in China: An Empirical Study Based on Panel Smooth Transition Regression Models.

PubMed

Wang, Zheng-Xin; Hao, Peng; Yao, Pei-Yi

2017-12-13

The non-linear relationship between provincial economic growth and carbon emissions is investigated by using panel smooth transition regression (PSTR) models. The research indicates that, on the condition of separately taking Gross Domestic Product per capita (GDPpc), energy structure (Es), and urbanisation level (Ul) as transition variables, three models all reject the null hypothesis of a linear relationship, i.e., a non-linear relationship exists. The results show that the three models all contain only one transition function but different numbers of location parameters. The model taking GDPpc as the transition variable has two location parameters, while the other two models separately considering Es and Ul as the transition variables both contain one location parameter. The three models applied in the study all favourably describe the non-linear relationship between economic growth and CO₂ emissions in China. It also can be seen that the conversion rate of the influence of Ul on per capita CO₂ emissions is significantly higher than those of GDPpc and Es on per capita CO₂ emissions.

Torque measurements reveal sequence-specific cooperative transitions in supercoiled DNA

PubMed Central

Oberstrass, Florian C.; Fernandes, Louis E.; Bryant, Zev

2012-01-01

B-DNA becomes unstable under superhelical stress and is able to adopt a wide range of alternative conformations including strand-separated DNA and Z-DNA. Localized sequence-dependent structural transitions are important for the regulation of biological processes such as DNA replication and transcription. To directly probe the effect of sequence on structural transitions driven by torque, we have measured the torsional response of a panel of DNA sequences using single molecule assays that employ nanosphere rotational probes to achieve high torque resolution. The responses of Z-forming d(pGpC)n sequences match our predictions based on a theoretical treatment of cooperative transitions in helical polymers. “Bubble” templates containing 50–100 bp mismatch regions show cooperative structural transitions similar to B-DNA, although less torque is required to disrupt strand–strand interactions. Our mechanical measurements, including direct characterization of the torsional rigidity of strand-separated DNA, establish a framework for quantitative predictions of the complex torsional response of arbitrary sequences in their biological context. PMID:22474350

Topics in Microeconometrics: Estimation of a Dynamic Model of Occupational Transitions, Wage and Non-Wage Benefits Cross Validation Bandwidth Selection for Derivatives of Various Dimensional Densities Testing the Additive Separability of the Teacher Value Added Effect Semiparametrically

ERIC Educational Resources Information Center

Baird, Matthew David

2012-01-01

I study three separate questions in this dissertation. In Chapter 1, I develop and estimate a structural dynamic model of occupation and job choice to test hypotheses of the importance of wages and non-wages and learning in occupational transitions, and find that wages are approximately 3 times as important as non-wage benefits in decisions and…

Preparation of functionalized zeolitic frameworks

DOEpatents

Yaghi, Omar M; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P

2012-11-20

The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

Preparation of functionalized zeolitic frameworks

DOEpatents

Yaghi, Omar M.; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P.

2014-08-19

The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

Preparation of functionalized zeolitic frameworks

DOEpatents

Yaghi, Omar M; Furukawa, Hiroyasu; Wang, Bo

2013-07-09

The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

Smooth School Transitions: Tips for Military Families

MedlinePlus

... family separation, and transition. Additional Information from HealthyChildren.org: Deployment and Children Military Families: Child Care Support ... CNN.com) Coming Together Around Military Families (zerotothree.org) FOCUS (Families OverComing Under Stress™) FOX News Talks ...

A facile approach for the fabrication of 3D flower-like Cu2S nanostructures on brass mesh with temperature-induced wetting transition for efficient oil-water separation

NASA Astrophysics Data System (ADS)

Niu, Lei; Kang, Zhixin

2017-11-01

3D flower-like Cu2S nanostructures on brass meshes have been fabricated for the first time, with a reversible wetting transition and excellent durability. In the present work, we demonstrated a simple and environmentally-benign method to fabricate the nanostructures utilizing an electrolyte containing CuSO4·5H2O, EDTA-2Na and CH3CSNH2. The superhydrophobicity was achieved by drying thoroughly at 200 °C, instead of using low surface energy materials. After annealing at 300 °C for 6 min, the superhydrophobic surface was oxidized and became superhydrophilic. However, the superhydrophobicity can be restored by heating at 200 °C for several hours. In simpler terms, the reversible wetting transition is responded to the temperature. Scanning electron microscopy, X-ray diffractometer, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the surfaces and analyze the wetting transition mechanism. Furthermore, different kinds of oily sewages were separated by as-prepared mesh with high separation efficiency. It is believed that this method should have a promising future in expanding the applications of copper alloys.

Aerodynamics and Percolation: Unfolding Laminar Separation Bubble on Airfoils

NASA Astrophysics Data System (ADS)

Traphan, Dominik; Wester, Tom T. B.; Gülker, Gerd; Peinke, Joachim; Lind, Pedro G.

2018-04-01

As a fundamental phenomenon of fluid mechanics, recent studies suggested laminar-turbulent transition belonging to the universality class of directed percolation. Here, the onset of a laminar separation bubble on an airfoil is analyzed in terms of the directed percolation model using particle image velocimetry data. Our findings indicate a clear significance of percolation models in a general flow situation beyond fundamental ones. We show that our results are robust against fluctuations of the parameter, namely, the threshold of turbulence intensity, that maps velocimetry data into binary cells (turbulent or laminar). In particular, this percolation approach enables the precise determination of the transition point of the laminar separation bubble, an important problem in aerodynamics.

Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

NASA Technical Reports Server (NTRS)

Padial, N.; Csanak, G.; Mckoy, B. V.; Langhoff, P. W.

1981-01-01

Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

Liquid absorbent solutions for separating nitrogen from natural gas

DOEpatents

Friesen, Dwayne T.; Babcock, Walter C.; Edlund, David J.; Lyon, David K.; Miller, Warren K.

2000-01-01

Nitrogen-absorbing and -desorbing compositions, novel ligands and transition metal complexes, and methods of using the same, which are useful for the selective separation of nitrogen from other gases, especially natural gas.

Generalized model for k -core percolation and interdependent networks

NASA Astrophysics Data System (ADS)

Panduranga, Nagendra K.; Gao, Jianxi; Yuan, Xin; Stanley, H. Eugene; Havlin, Shlomo

2017-09-01

Cascading failures in complex systems have been studied extensively using two different models: k -core percolation and interdependent networks. We combine the two models into a general model, solve it analytically, and validate our theoretical results through extensive simulations. We also study the complete phase diagram of the percolation transition as we tune the average local k -core threshold and the coupling between networks. We find that the phase diagram of the combined processes is very rich and includes novel features that do not appear in the models studying each of the processes separately. For example, the phase diagram consists of first- and second-order transition regions separated by two tricritical lines that merge and enclose a two-stage transition region. In the two-stage transition, the size of the giant component undergoes a first-order jump at a certain occupation probability followed by a continuous second-order transition at a lower occupation probability. Furthermore, at certain fixed interdependencies, the percolation transition changes from first-order → second-order → two-stage → first-order as the k -core threshold is increased. The analytic equations describing the phase boundaries of the two-stage transition region are set up, and the critical exponents for each type of transition are derived analytically.

The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

PubMed

Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

2007-01-18

Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

Effects of ions on the solubility transition and the phase-separation of N-isopropylacrylamide in water.

PubMed

Sasaki, Shigeo; Okabe, Satoshi

2011-11-10

The effects of NaCl, NaOH, and HCl on the solubility transition and the phase-separation of N-isopropylacrylamide (NIPA) were investigated for the purpose of clarifying the physicochemical mechanism of salting-out and salting-in phenomena. The discrete change in the solubility of NIPA in the salt-free water at the solubility transition (reported in J. Phys. Chem. B 2010, 114, 14995-15002) decreased with the addition of HCl and disappeared in the HCl solutions at concentrations higher than 2 M, while it increased with additions of NaOH and NaCl. A difference in NIPA concentration between the phase-separated solutions decreases with the addition of HCl and increases with additions of NaOH and NaCl. Partition coefficients of HCl in the phase-separated NIPA-rich solutions are higher than those in the NIPA poor solutions, while partition coefficients of NaCl and NaOH between the NIPA-rich and -poor solutions have trends opposite to those of HCl. The present results clearly indicate that the HCl favors the dehydrated NIPA and stabilizes the H(2)O-poor state of the NIPA molecule more than NaCl.

A complex-lamellar description of boundary layer transition

NASA Astrophysics Data System (ADS)

Kolla, Maureen Louise

Flow transition is important, in both practical and phenomenological terms. However, there is currently no method for identifying the spatial locations associated with transition, such as the start and end of intermittency. The concept of flow stability and experimental correlations have been used, however, flow stability only identifies the location where disturbances begin to grow in the laminar flow and experimental correlations can only give approximations as measuring the start and end of intermittency is difficult. Therefore, the focus of this work is to construct a method to identify the start and end of intermittency, for a natural boundary layer transition and a separated flow transition. We obtain these locations by deriving a complex-lamellar description of the velocity field that exists between a fully laminar and fully turbulent boundary condition. Mathematically, this complex-lamellar decomposition, which is constructed from the classical Darwin-Lighthill-Hawthorne drift function and the transport of enstrophy, describes the flow that exists between the fully laminar Pohlhausen equations and Prandtl's fully turbulent one seventh power law. We approximate the difference in enstrophy density between the boundary conditions using a power series. The slope of the power series is scaled by using the shape of the universal intermittency distribution within the intermittency region. We solve the complex-lamellar decomposition of the velocity field along with the slope of the difference in enstrophy density function to determine the location of the laminar and turbulent boundary conditions. Then from the difference in enstrophy density function we calculate the start and end of intermittency. We perform this calculation on a natural boundary layer transition over a flat plate for zero pressure gradient flow and for separated shear flow over a separation bubble. We compare these results to existing experimental results and verify the accuracy of our transition model.

Gardner Transition in Physical Dimensions

NASA Astrophysics Data System (ADS)

Hicks, C. L.; Wheatley, M. J.; Godfrey, M. J.; Moore, M. A.

2018-06-01

The Gardner transition is the transition that at mean-field level separates a stable glass phase from a marginally stable phase. This transition has similarities with the de Almeida-Thouless transition of spin glasses. We have studied a well-understood problem, that of disks moving in a narrow channel, which shows many features usually associated with the Gardner transition. We show that some of these features are artifacts that arise when a disk escapes its local cage during the quench to higher densities. There is evidence that the Gardner transition becomes an avoided transition, in that the correlation length becomes quite large, of order 15 particle diameters, even in our quasi-one-dimensional system.

Measuring the performance of transit relative to livability.

DOT National Transportation Integrated Search

2013-03-01

This project sought to understand the relationship between urban form, transit service characteristics, and ridership measured at the stop level. Most previous work in this area has looked at these issues separately, by either linking system performa...

Aerodynamic study of a small wind turbine with emphasis on laminar and transition flows

NASA Astrophysics Data System (ADS)

Niculescu, M. L.; Cojocaru, M. G.; Crunteanu, D. E.

2016-06-01

The wind energy is huge but unfortunately, wind turbines capture only a little part of this enormous green energy. Furthermore, it is impossible to put multi megawatt wind turbines in the cities because they generate a lot of noise and discomfort. Instead, it is possible to install small Darrieus and horizontal-axis wind turbines with low tip speed ratios in order to mitigate the noise as much as possible. Unfortunately, the flow around this wind turbine is quite complex because the run at low Reynolds numbers. Therefore, this flow is usually a mixture of laminar, transition and laminar regimes with bubble laminar separation that is very difficult to simulate from the numerical point of view. Usually, transition and laminar regimes with bubble laminar separation are ignored. For this reason, this paper deals with laminar and transition flows in order to provide some brightness in this field.

A Summative Program Evaluation of a Comprehensive 9th Grade Transition Program

ERIC Educational Resources Information Center

Roybal, Victoria M.

2011-01-01

The transition from 8th grade to 9th grade is one that is replete with challenges for students, especially for minority students who live in economically disadvantaged communities. One low-income, high minority comprehensive high school in the western United States implemented five separate strategies to create a freshman transition program to aid…

Flow-separation patterns on symmetric forebodies

NASA Technical Reports Server (NTRS)

Keener, Earl R.

1986-01-01

Flow-visualization studies of ogival, parabolic, and conical forebodies were made in a comprehensive investigation of the various types of flow patterns. Schlieren, vapor-screen, oil-flow, and sublimation flow-visualization tests were conducted over an angle-of-attack range from 0 deg. to 88 deg., over a Reynolds-number range from 0.3X10(6) to 2.0X10(6) (based on base diameter), and over a Mach number range from 0.1 to 2. The principal effects of angle of attack, Reynolds number, and Mach number on the occurrence of vortices, the position of vortex shedding, the principal surface-flow-separation patterns, the magnitude of surface-flow angles, and the extent of laminar and turbulent flow for symmetric, asymmetric, and wake-like flow-separation regimes are presented. It was found that the two-dimensional cylinder analogy was helpful in a qualitative sense in analyzing both the surface-flow patterns and the external flow field. The oil-flow studies showed three types of primary separation patterns at the higher Reynolds numbers owing to the influence of boundary-layer transition. The effect of angle of attack and Reynolds number is to change the axial location of the onset and extent of the primary transitional and turbulent separation regions. Crossflow inflectional-instability vortices were observed on the windward surface at angles of attack from 5 deg. to 55 deg. Their effect is to promote early transition. At low angles of attack, near 10 deg., an unexpected laminar-separation bubble occurs over the forward half of the forebody. At high angles of attack, at which vortex asymmetry occurs, the results support the proposition that the principal cause of vortex asymmetry is the hydrodynamic instability of the inviscid flow field. On the other hand, boundary-layer asymmetries also occur, especially at transitional Reynolds numbers. The position of asymmetric vortex shedding moves forward with increasing angle of attack and with increasing Reynolds number, and moves rearward with increasing Mach number.

Parental Separation/Divorce and Adolescents: An Examination of Factors Mediating Adaptation.

ERIC Educational Resources Information Center

Farber, Stephanie S.; And Others

Parental separation or divorce is a life transition experienced by a significant number of adolescents every year. To examine the relationship between differences in current adjustment and a number of demographic, personal, and situational factors, 65 college students, aged 17-23 who had experienced parental separation or divorce between the ages…

26 CFR 1.904(f)-12T - Transition rules (temporary).

Code of Federal Regulations, 2010 CFR

2010-04-01

... services income or general limitation income. To the extent that a taxpayer has a balance in any separate... balance in any separate limitation loss or overall foreign loss account in a pre-2007 separate category... such balance, or balances, shall be allocated on the first day of the taxpayer's next taxable year to...

Is Separation Anxiety in Adolescents and Parents Related to Parental Differentiation of Self?

ERIC Educational Resources Information Center

Peleg, Ora; Miller, Paul; Yitzhak, Meital

2015-01-01

The current study examined the relationship between separation anxiety in adolescents after their transition to middle school, on the one hand, and differentiation of self and separation anxiety in their parents, on the other hand. The sample included 88 adolescents from northern Israel, together with their biological parents. Adolescents'…

Saying Goodbye: An Investigation into Parent-Infant Separation Behaviours on Arrival in Childcare

ERIC Educational Resources Information Center

Jovanovic, Jessie

2011-01-01

The goal of this small-scale study was to investigate how parental separation behaviours affect the transitional behaviour of infants aged 6-18 months. Thirty parent-infant pairs were observed during the separation process across three metropolitan childcare centres in Adelaide, South Australia. Observed interactions with both their infants and…

26 CFR 1.904(f)-12T - Transition rules (temporary).

Code of Federal Regulations, 2011 CFR

2011-04-01

... separate categories for passive income, certain dividends from a DISC or former DISC, taxable income... separate limitation loss or overall foreign loss incurred in a pre-2007 separate category for passive... (as defined in § 1.904-7T(g)(1)(ii)) for passive income, certain dividends from a DISC or former DISC...

Natural laminar flow and airplane stability and control

NASA Technical Reports Server (NTRS)

Vandam, Cornelis P.

1986-01-01

Location and mode of transition from laminar to turbulent boundary layer flow have a dominant effect on the aerodynamic characteristics of an airfoil section. The influences of these parameters on the sectional lift and drag characteristics of three airfoils are examined. Both analytical and experimental results demonstrate that when the boundary layer transitions near the leading edge as a result of surface roughness, extensive trailing-edge separation of the turbulent boundary layer may occur. If the airfoil has a relatively sharp leading-edge, leading-edge stall due to laminar separation can occur after the leading-edge suction peak is formed. These two-dimensional results are used to examine the effects of boundary layer transition behavior on airplane longitudinal and lateral-directional stability and control.

Isotope separation by photodissociation of Van der Waal's molecules

DOEpatents

Lee, Yuan T.

1977-01-01

A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

Active control of noise amplification in the flow over a square leading-edge flat plate utilizing DBD plasma actuator

NASA Astrophysics Data System (ADS)

Yadong, HUANG; Benmou, ZHOU

2018-05-01

Perturbation is generally considered as the flow noise, and its energy can gain transient growth in the separation bubble. The amplified perturbations may cause unstable Kelvin–Helmohltz vortices which induce the three-dimensional transition. Active control of noise amplification via dielectric barrier discharge plasma actuator in the flow over a square leading-edge flat plate is numerically studied. The actuator is installed near the plate leading-edge where the separation bubble is formed. The maximum energy amplification of perturbations is positively correlated with the separation bubble scale which decreases with the increasing control parameters. As the magnitude of noise amplification is reduced, the laminar-turbulent transition is successfully suppressed.

Electrophoretic-like gating used to control metal-insulator transitions in electronically phase separated manganite wires.

PubMed

Guo, Hangwen; Noh, Joo H; Dong, Shuai; Rack, Philip D; Gai, Zheng; Xu, Xiaoshan; Dagotto, Elbio; Shen, Jian; Ward, T Zac

2013-08-14

Electronically phase separated manganite wires are found to exhibit controllable metal-insulator transitions under local electric fields. The switching characteristics are shown to be fully reversible, polarity independent, and highly resistant to thermal breakdown caused by repeated cycling. It is further demonstrated that multiple discrete resistive states can be accessed in a single wire. The results conform to a phenomenological model in which the inherent nanoscale insulating and metallic domains are rearranged through electrophoretic-like processes to open and close percolation channels.

Experimental studies of the Eppler 61 airfoil at low Reynolds numbers

NASA Technical Reports Server (NTRS)

Burns, T. F.; Mueller, T. J.

1982-01-01

The results of an experimental study to document the effects of separation and transition on the performance of an airfoil designed for low Reynolds number operation are presented. Lift, drag and flow visualization data were obtained for the Eppler 61 airfoil section for chord Reynolds numbers from about 30,000 to over 200,000. Smoke flow visualization was employed to document the boundary layer behavior and was correlated with the Eppler airfoil design and analysis computer program. Laminar separation, transition and turbulent reattachment had significant effects on the performance of this airfoil.

Venus Transit

NASA Image and Video Library

2012-06-05

It appeared that New Yorkers were not going to be able to see the transit of the planet Venus across the Sun, but just before the transit was over the sun broke through the clouds and Yvette Lee Kang was able to catch a glimpse of the transit on Tuesday, June 5, 2012 in New York. A transit of Venus occurs when the planet passes directly between the sun and earth. This alignment is rare, coming in pairs that are eight years apart but separated by over a century. The next Venus transit will be in December 2117. Photo Credit: (NASA/Bill Ingalls)

Advanced boundary layer transition measurement methods for flight applications

NASA Technical Reports Server (NTRS)

Holmes, B. J.; Croom, C. C.; Gail, P. D.; Manuel, G. S.; Carraway, D. L.

1986-01-01

In modern laminar flow flight research, it is important to understand the specific cause(s) of laminar to turbulent boundary-layer transition. Such information is crucial to the exploration of the limits of practical application of laminar flow for drag reduction on aircraft. The transition modes of interest in current flight investigations include the viscous Tollmien-Schlichting instability, the inflectional instability at laminar separation, and the crossflow inflectional instability, as well as others. This paper presents the results to date of research on advanced devices and methods used for the study of laminar boundary-layer transition phenomena in the flight environment. Recent advancements in the development of arrayed hot-film devices and of a new flow visualization method are discussed. Arrayed hot-film devices have been designed to detect the presence of laminar separation, and of crossflow vorticity. The advanced flow visualization method utilizes color changes in liquid-crystal coatings to detect boundary-layer transition at high altitude flight conditions. Flight and wind tunnel data are presented to illustrate the design and operation of these advanced methods. These new research tools provide information on disturbance growth and transition mode which is essential to furthering our understanding of practical design limits for applications of laminar flow technology.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

Cold-gas experiments to study the flow separation characteristics of a dual-bell nozzle during its transition modes

NASA Astrophysics Data System (ADS)

Verma, S. B.; Stark, R.; Nuerenberger-Genin, C.; Haidn, O.

2010-06-01

An experimental investigation has been carried out to study the effect of test environment on transition characteristics and the flow unsteadiness associated with the transition modes of a dual-bell nozzle. Cold-gas tests using gaseous nitrogen were carried out in (i) a horizontal test-rig with nozzle exhausting into atmospheric conditions and, (ii) a high altitude simulation chamber with nozzle operation under self-evacuation mode. Transient tests indicate that increasing δP 0/ δt (the rate of stagnation chamber pressure change) reduces the amplitude of pressure fluctuations of the separation shock at the wall inflection point. This is preferable from the viewpoint of lowering the possible risk of any structural failure during the transition mode. Sea-level tests show 15-17% decrease in the transition nozzle pressure ratio (NPR) during subsequent tests in a single run primarily due to frost formation in the nozzle extension up to the wall inflection location. Frost reduces the wall inflection angle and hence, the transition NPR. However, tests inside the altitude chamber show nearly constant NPR value during subsequent runs primarily due to decrease in back temperature with decrease in back pressure that prevents any frost formation.

Creating History: By Design or by Default.

ERIC Educational Resources Information Center

Baugher, Shirley L.

1989-01-01

The author presents social demographic forecasts for the future. She examines social, economic, and political transitions in U.S. society separately and argues that the transitions that society makes depend ultimately on the values upon which individuals choose to act. (CH)

47 CFR 90.676 - Transition administrator for reconfiguration of the 806-824/851-869 MHz band in order to separate...

Code of Federal Regulations, 2010 CFR

2010-10-01

... their systems and ensuring that estimates contain a firm work schedule. The Transition Administrator... available to eligible applicants in the Public Safety or Critical Infrastructure Industry Categories as set...

The NASA Low-Pressure Turbine Flow Physics Program

NASA Technical Reports Server (NTRS)

Ashpis, David E.

1998-01-01

An overview of the NASA Lewis Low-Pressure Turbine (LPT) Flow Physics Program will be presented. The program was established in response to the aero-engine industry's need for improved LPT efficiency and designs. Modern jet engines have four to seven LPT stages, significantly contributing to engine weight. In addition, there is a significant efficiency degradation between takeoff and cruise conditions, of up to 2 points. Reducing the weight and part count of the LPT and minimizing the efficiency degradation will translate into fuel savings. Accurate prediction methods of LPT flows and losses are needed to accomplish those improvements. The flow in LPT passages is at low Reynolds number, and is dominated by interplay of three basic mechanisms: transition, separation and wake interaction. The affecting parameters traditionally considered are Reynolds number, freestream turbulence intensity, wake frequency parameter, and the pressure distribution (loading). Three-dimensional effects and additional parameters, particularly turbulence characteristics like length scales, spectra and other statistics, as well as wake turbulence intensity and properties also play a role. The flow of most interest is on the suction surface, where large losses are generated as the flow tends to separate at the low Reynolds numbers. Ignoring wakes, a common flow scenario, there is laminar separation, followed by transition on the separation bubble and turbulent reattachment. If transition starts earlier the separation will be eliminated and the boundary layer will be attached leading to the well known bypass transition issues. In contrast, transition over a separation bubble is closer to free shear layer transition and was not investigated as well, particularly in the turbine environment. Unsteadiness created by wakes complicates the picture. Wakes induce earlier transition, and the calmed regions trailing the induced turbulent spots can delay or eliminate separation via shear stress modification. Three-dimensional flow physics and geometry will have strong effects. Altogether a very complex and challenging problem emerges. The objective of the program is to provide improved models and physical understanding of the complex flow, which are essential for accurate prediction of flow and losses in the LPT. Experimental, computational and analytical work as complementing and augmenting approaches are used. The program involves industry, universities and research institutes, and other government laboratories. It is characterized by strong interaction among participants, quick dissemination of results, and responsiveness to industry's needs. The presentation will describe the work elements. Highlighting some activities in progress are experiments on simulated blade suction surface in low-speed wind tunnels, on curved wall, and on a flat-plate, both with pressure gradient. In the area of computation, assessment of existing models is performed using RANS (Reynolds Averaged Navier Stokes) simulations. Laminar flow DNS was completed. Analytical studies of instability and receptivity in attached and separated flows were started. In the near future the program is moving to include wake effects and development of improved modeling. Experimental work in preparation stages are: (1) Addition of wakes to the curved tunnel experiment; (2) Low-speed rotating rig experiment on GE90 engine LPT; and (3) Transonic cascade. In the area of computation, it is expected to move from model assessment towards development of improved models. In addition, a new project of Large Eddy Simulation (LES) of LPT is to begin and will provide numerical data bases. It is planned to implement the emerging improved models in a multistage turbomachinery code and to validate against the GE90 engine LPT.

Separation: High School to College.

ERIC Educational Resources Information Center

Brody, Michael; And Others

The transition from high school senior to college freshman reflects the emergence of the adolescent into the young adult and can result in separation anxiety for parent and senior. In order to support the parents and seniors, a seminar on the topic of separation was given to parents and seniors by a child psychiatrist and two high school college…

Systems and methods for separating a multiphase fluid

NASA Technical Reports Server (NTRS)

Weislogel, Mark M. (Inventor); Thomas, Evan A. (Inventor); Graf, John C. (Inventor)

2011-01-01

Apparatus and methods for separating a fluid are provided. The apparatus can include a separator and a collector having an internal volume defined at least in part by one or more surfaces narrowing toward a bottom portion of the volume. The separator can include an exit port oriented toward the bottom portion of the volume. The internal volume can receive a fluid expelled from the separator into a flow path in the collector and the flow path can include at least two directional transitions within the collector.

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

Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora, E-mail: aurora.nogales@csic.es

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{sub ODT}, the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chainmore » 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.« less

Energetics of bacterial photosynthesis.

PubMed

Lebard, David N; Matyushov, Dmitry V

2009-09-10

We report the results of extensive numerical simulations and theoretical calculations of electronic transitions in the reaction center of Rhodobacter sphaeroides photosynthetic bacterium. The energetics and kinetics of five electronic transitions related to the kinetic scheme of primary charge separation have been analyzed and compared to experimental observations. Nonergodic formulation of the reaction kinetics is required for the calculation of the rates due to a severe breakdown of the system ergodicity on the time scale of primary charge separation, with the consequent inapplicability of the standard canonical prescription to calculate the activation barrier. Common to all reactions studied is a significant excess of the charge-transfer reorganization energy from the width of the energy gap fluctuations over that from the Stokes shift of the transition. This property of the hydrated proteins, breaking the linear response of the thermal bath, allows the reaction center to significantly reduce the reaction free energy of near-activationless electron hops and thus raise the overall energetic efficiency of the biological charge-transfer chain. The increase of the rate of primary charge separation with cooling is explained in terms of the temperature variation of induction solvation, which dominates the average donor-acceptor energy gap for all electronic transitions in the reaction center. It is also suggested that the experimentally observed break in the Arrhenius slope of the primary recombination rate, occurring near the temperature of the dynamical transition in proteins, can be traced back to a significant drop of the solvent reorganization energy close to that temperature.

Jet-cooled laser-induced fluorescence spectroscopy of cyclohexoxy: rotational and fine structure of molecules in nearly degenerate electronic States.

PubMed

Liu, Jinjun; Miller, Terry A

2014-12-26

The rotational structure of the previously observed B̃(2)A' ← X̃(2)A″ and B̃(2)A' ← Ã(2)A' laser-induced fluorescence spectra of jet-cooled cyclohexoxy radical (c-C6H11O) [ Zu, L.; Liu, J.; Tarczay, G.; Dupré, P; Miller, T. A. Jet-cooled laser spectroscopy of the cyclohexoxy radical. J. Chem. Phys. 2004 , 120 , 10579 ] has been analyzed and simulated using a spectroscopic model that includes the coupling between the nearly degenerate X̃ and à states separated by ΔE. The rotational and fine structure of these two states is reproduced by a 2-fold model using one set of molecular constants including rotational constants, spin-rotation constants (ε's), the Coriolis constant (Aζt), the quenched spin-orbit constant (aζed), and the vibronic energy separation between the two states (ΔE0). The energy level structure of both states can also be reproduced using an isolated-state asymmetric top model with rotational constants and effective spin-rotation constants (ε's) and without involving Coriolis and spin-orbit constants. However, the spin-orbit interaction introduces transitions that have no intensity using the isolated-state model but appear in the observed spectra. The line intensities are well simulated using the 2-fold model with an out-of-plane (b-) transition dipole moment for the B̃ ← X̃ transitions and in-plane (a and c) transition dipole moment for the B̃ ← à transitions, requiring the symmetry for the X̃ (Ã) state to be A″ (A'), which is consistent with a previous determination and opposite to that of isopropoxy, the smallest secondary alkoxy radical. The experimentally determined Ã-X̃ separation and the energy level ordering of these two states with different (A' and A″) symmetries are consistent with quantum chemical calculations. The 2-fold model also enables the independent determination of the two contributions to the Ã-X̃ separation: the relativistic spin-orbit interaction (magnetic effect) and the nonrelativistic vibronic separation between the lowest vibrational energy levels of these two states due to both electrostatic interaction (Coulombic effect) and difference in zero-point energies (kinetic effect).

Electronic and structural aspects of spin transitions observed by optical microscopy. The case of [Fe(ptz)6](BF4)2.

PubMed

Chong, Christian; Mishra, Haritosh; Boukheddaden, Kamel; Denise, Stéphane; Bouchez, Guillaume; Collet, Eric; Ameline, Jean-Claude; Naik, Anil D; Garcia, Yann; Varret, François

2010-02-11

The colorimetric analysis of images recorded with an optical microscope during the onset of the spin crossover transformation allows monitoring separately the involved electronic and structural aspects, through the separation of resonant absorption and scattering effects. Complementary information can also be obtained by using the polarized modes of the microscope. These potentialities are illustrated by the observation of [Fe(ptz)(6)](BF(4))(2) single crystals during the onset of the thermal transitions in the 110-140 K range. We characterized the interplay between the electronic (HS <--> LS) and structural (order <--> disorder) transformations. Elastic stresses and mechanical effects (hopping, self-cleavage) generated by the volume change upon electronic transition are also illustrated, with their impact on the photoswitching properties of the crystals.

The effects of tonal and broadband acoustic excitation on the transition process within a laminar separation bubble

NASA Astrophysics Data System (ADS)

Yarusevych, Serhiy; Kurelek, John; Kotsonis, Marios

2017-11-01

The effects of controlled acoustic excitation on the transition process in a laminar separation bubble formed on the suction side of a NACA 0018 airfoil at a chord Reynolds number of 125,000 and an angle of attack of 4 degrees are studied experimentally. The investigation is carried out using time-resolved, planar, two-component Particle Image Velocimetry. Two types of excitation are considered: (i) tonal excitation at the frequency of the most unstable disturbances in the natural flow, and (ii) broadband excitation consisting bandpass filtered to the natural unstable frequency range, modelling two common types of airfoil self-noise production. For equal energy input levels, the results show that tonal and broadband types of excitation have equivalent effects on the mean flow field. Specifically, both cause the streamwise extent and height of the bubble to decrease. However, further analysis reveals notable differences in the underlying physics. For the tonal case, the transition process is dominated by the growth of disturbances at the excitation frequency that damps the growth of all other disturbances, leading to the formation of strongly coherent vortices in the aft portion of the separation bubble. On the other hand, broadband excitation promotes more moderate growth of all disturbances within the unstable frequency band, producing less coherent shear layer structures that experience earlier breakdown. Thus, the frequency content of acoustic excitation has a strong influence on the transition process in laminar separation bubbles. The authors gratefully acknowledge the Natural Sciences and Engineering Research Council of Canada (NSERC) for funding this work.

Asymmetry-symmetry transition of double-sided adhesive tapes

NASA Astrophysics Data System (ADS)

Yamaguchi, Tetsuo; Muroo, Hiroyuki; Sumino, Yutaka; Doi, Masao

2012-06-01

We report on the debonding process of a double-sided adhesive tape sandwiched between two glass plates. When the glass plates are separated from each other at a constant rate, a highly asymmetric extension of top and bottom adhesive layers and bending of the inner film are observed first. As the separation proceeds, the elongation of both layers becomes symmetric, and the inner film becomes flat again. When this happens, there appears a local maximum in the force-displacement curve. We explain this asymmetry-symmetry transition and discuss the role of the bimodal force-displacement relation of each adhesive layer. We also discuss the effect of the inner film thickness and the separation rate on the debonding behavior, which causes undesirable early detachment of the double-sided adhesive tape in a certain condition.

Plume effects on the flow around a blunted cone at hypersonic speeds

NASA Technical Reports Server (NTRS)

Atcliffe, P.; Kumar, D.; Stollery, J. L.

1992-01-01

Tests at M = 8.2 show that a simulated rocket plume at the base of a blunted cone can cause large areas of separated flow, with dramatic effects on the heat transfer rate distribution. The plume was simulated by solid discs of varying sizes or by an annular jet of gas. Flow over the cone without a plume is fully laminar and attached. Using a large disc, the boundary layer is laminar at separation at the test Reynolds number. Transition occurs along the separated shear layer and the boundary layer quickly becomes turbulent. The reduction in heat transfer associated with a laminar separated region is followed by rising values as transition occurs and the heat transfer rates towards the rear of the cone substantially exceed the values obtained without a plume. With the annular jet or a small disc, separation occurs much further aft, so that heat transfer rates at the front of the cone are comparable with those found without a plume. Downstream of separation the shear layer now remains laminar and the heat transfer rates to the surface are significantly lower than the attached flow values.

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

Cadiz, Fabian, E-mail: cadiz@insa-toulouse.fr; Tricard, Simon; Gay, Maxime

Developments in optoelectronics and spin-optronics based on transition metal dichalcogenide monolayers (MLs) need materials with efficient optical emission and well-defined transition energies. In as-exfoliated MoS{sub 2} MLs, the photoluminescence (PL) spectra even at low temperature consist typically of broad, overlapping contributions from neutral, charged excitons (trions) and localized states. Here, we show that in superacid treated MoS{sub 2} MLs, the PL intensity increases by up to 60 times at room temperature. The neutral and charged exciton transitions are spectrally well separated in PL and reflectivity at T = 4 K, with linewidth for the neutral exciton of 15 meV, but both transitions have similarmore » intensities compared to the ones in as-exfoliated MLs at the same temperature. Time resolved experiments uncover picoseconds recombination dynamics analyzed separately for charged and neutral exciton emissions. Using the chiral interband selection rules, we demonstrate optically induced valley polarization for both complexes and valley coherence for only the neutral exciton.« less

Energy exchange between a laser beam and charged particles using inverse transition radiation and method for its use

DOEpatents

Kimura, Wayne D.; Romea, Richard D.; Steinhauer, Loren C.

1998-01-01

A method and apparatus for exchanging energy between relativistic charged particles and laser radiation using inverse diffraction radiation or inverse transition radiation. The beam of laser light is directed onto a particle beam by means of two optical elements which have apertures or foils through which the particle beam passes. The two apertures or foils are spaced by a predetermined distance of separation and the angle of interaction between the laser beam and the particle beam is set at a specific angle. The separation and angle are a function of the wavelength of the laser light and the relativistic energy of the particle beam. In a diffraction embodiment, the interaction between the laser and particle beams is determined by the diffraction effect due to the apertures in the optical elements. In a transition embodiment, the interaction between the laser and particle beams is determined by the transition effect due to pieces of foil placed in the particle beam path.

Volume-wise destruction of the antiferromagnetic Mott insulating state through quantum tuning.

PubMed

Frandsen, Benjamin A; Liu, Lian; Cheung, Sky C; Guguchia, Zurab; Khasanov, Rustem; Morenzoni, Elvezio; Munsie, Timothy J S; Hallas, Alannah M; Wilson, Murray N; Cai, Yipeng; Luke, Graeme M; Chen, Bijuan; Li, Wenmin; Jin, Changqing; Ding, Cui; Guo, Shengli; Ning, Fanlong; Ito, Takashi U; Higemoto, Wataru; Billinge, Simon J L; Sakamoto, Shoya; Fujimori, Atsushi; Murakami, Taito; Kageyama, Hiroshi; Alonso, Jose Antonio; Kotliar, Gabriel; Imada, Masatoshi; Uemura, Yasutomo J

2016-08-17

RENiO3 (RE=rare-earth element) and V2O3 are archetypal Mott insulator systems. When tuned by chemical substitution (RENiO3) or pressure (V2O3), they exhibit a quantum phase transition (QPT) between an antiferromagnetic Mott insulating state and a paramagnetic metallic state. Because novel physics often appears near a Mott QPT, the details of this transition, such as whether it is first or second order, are important. Here, we demonstrate through muon spin relaxation/rotation (μSR) experiments that the QPT in RENiO3 and V2O3 is first order: the magnetically ordered volume fraction decreases to zero at the QPT, resulting in a broad region of intrinsic phase separation, while the ordered magnetic moment retains its full value until it is suddenly destroyed at the QPT. These findings bring to light a surprising universality of the pressure-driven Mott transition, revealing the importance of phase separation and calling for further investigation into the nature of quantum fluctuations underlying the transition.

Volume-wise destruction of the antiferromagnetic Mott insulating state through quantum tuning

NASA Astrophysics Data System (ADS)

Frandsen, Benjamin A.; Liu, Lian; Cheung, Sky C.; Guguchia, Zurab; Khasanov, Rustem; Morenzoni, Elvezio; Munsie, Timothy J. S.; Hallas, Alannah M.; Wilson, Murray N.; Cai, Yipeng; Luke, Graeme M.; Chen, Bijuan; Li, Wenmin; Jin, Changqing; Ding, Cui; Guo, Shengli; Ning, Fanlong; Ito, Takashi U.; Higemoto, Wataru; Billinge, Simon J. L.; Sakamoto, Shoya; Fujimori, Atsushi; Murakami, Taito; Kageyama, Hiroshi; Alonso, Jose Antonio; Kotliar, Gabriel; Imada, Masatoshi; Uemura, Yasutomo J.

2016-08-01

RENiO3 (RE=rare-earth element) and V2O3 are archetypal Mott insulator systems. When tuned by chemical substitution (RENiO3) or pressure (V2O3), they exhibit a quantum phase transition (QPT) between an antiferromagnetic Mott insulating state and a paramagnetic metallic state. Because novel physics often appears near a Mott QPT, the details of this transition, such as whether it is first or second order, are important. Here, we demonstrate through muon spin relaxation/rotation (μSR) experiments that the QPT in RENiO3 and V2O3 is first order: the magnetically ordered volume fraction decreases to zero at the QPT, resulting in a broad region of intrinsic phase separation, while the ordered magnetic moment retains its full value until it is suddenly destroyed at the QPT. These findings bring to light a surprising universality of the pressure-driven Mott transition, revealing the importance of phase separation and calling for further investigation into the nature of quantum fluctuations underlying the transition.

Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations.

PubMed

Wu, Guangfen; Li, Zi; Zhang, Xu; Lu, Gang

2014-08-07

Charge separation and exciton dynamics play a crucial role in determining the performance of excitonic photovoltaics. Using time-dependent density functional theory with a range-separated exchange-correlation functional as well as nonadiabatic ab initio molecular dynamics, we have studied the formation and dynamics of charge-transfer (CT) excitons at polymer/ZnO interface. The interfacial atomic structure, exciton density of states and conversions between exciton species are examined from first-principles. The exciton dynamics exhibits both adiabatic and nonadiabatic characters. While the adiabatic transitions are facilitated by C═C vibrations along the polymer (P3HT) backbone, the nonadiabatic transitions are realized by exciton hopping between the excited states. We find that the localized ZnO surface states lead to localized low-energy CT states and poor charge separation. In contrast, the surface states of crystalline C60 are indistinguishable from the bulk states, resulting in delocalized CT states and efficient charge separation in polymer/fullerene (P3HT/PCBM) heterojunctions. The hot CT states are found to cool down in an ultrafast time scale and may not play a major role in charge separation of P3HT/ZnO. Finally we suggest that the dimensions of nanostructured acceptors can be tuned to obtain both efficient charge separation and high open circuit voltages.

Theoretical Analysis of Competing Conformational Transitions in Superhelical DNA

PubMed Central

Zhabinskaya, Dina; Benham, Craig J.

2012-01-01

We develop a statistical mechanical model to analyze the competitive behavior of transitions to multiple alternate conformations in a negatively supercoiled DNA molecule of kilobase length and specified base sequence. Since DNA superhelicity topologically couples together the transition behaviors of all base pairs, a unified model is required to analyze all the transitions to which the DNA sequence is susceptible. Here we present a first model of this type. Our numerical approach generalizes the strategy of previously developed algorithms, which studied superhelical transitions to a single alternate conformation. We apply our multi-state model to study the competition between strand separation and B-Z transitions in superhelical DNA. We show this competition to be highly sensitive to temperature and to the imposed level of supercoiling. Comparison of our results with experimental data shows that, when the energetics appropriate to the experimental conditions are used, the competition between these two transitions is accurately captured by our algorithm. We analyze the superhelical competition between B-Z transitions and denaturation around the c-myc oncogene, where both transitions are known to occur when this gene is transcribing. We apply our model to explore the correlation between stress-induced transitions and transcriptional activity in various organisms. In higher eukaryotes we find a strong enhancement of Z-forming regions immediately 5′ to their transcription start sites (TSS), and a depletion of strand separating sites in a broad region around the TSS. The opposite patterns occur around transcript end locations. We also show that susceptibility to each type of transition is different in eukaryotes and prokaryotes. By analyzing a set of untranscribed pseudogenes we show that the Z-susceptibility just downstream of the TSS is not preserved, suggesting it may be under selection pressure. PMID:22570598

Aqueous-Based Fabrication of Low-VOC Nanostructured Block Copolymer Films as Potential Marine Antifouling Coatings.

PubMed

Kim, Kris S; Gunari, Nikhil; MacNeil, Drew; Finlay, John; Callow, Maureen; Callow, James; Walker, Gilbert C

2016-08-10

The ability to fabricate nanostructured films by exploiting the phenomenon of microphase separation has made block copolymers an invaluable tool for a wide array of coating applications. Standard approaches to engineering nanodomains commonly involve the application of organic solvents, either through dissolution or annealing protocols, resulting in the release of volatile organic compounds (VOCs). In this paper, an aqueous-based method of fabricating low-VOC nanostructured block copolymer films is presented. The reported procedure allows for the phase transfer of water insoluble triblock copolymer, poly(styrene-block-2 vinylpyridine-block-ethylene oxide) (PS-b-P2VP-b-PEO), from a water immiscible phase to an aqueous environment with the assistance of a diblock copolymeric phase transfer agent, poly(styrene-block-ethylene oxide) (PS-b-PEO). Phase transfer into the aqueous phase results in self-assembly of PS-b-P2VP-b-PEO into core-shell-corona micelles, which are characterized by dynamic light scattering techniques. The films that result from coating the micellar solution onto Si/SiO2 surfaces exhibit nanoscale features that disrupt the ability of a model foulant, a zoospore of Ulva linza, to settle. The multilayered architecture consists of a pH-responsive P2VP-"shell" which can be stimulated to control the size of these features. The ability of these nanostructured thin films to resist protein adsorption and serve as potential marine antifouling coatings is supported through atomic force microscopy (AFM) and analysis of the settlement of Ulva linza zoospore. Field trials of the surfaces in a natural environment show the inhibition of macrofoulants for 1 month.

Rinse-resistant superhydrophobic block copolymer fabrics by electrospinning, electrospraying and thermally-induced self-assembly

NASA Astrophysics Data System (ADS)

Wu, Jie; Li, Xin; Wu, Yang; Liao, Guoxing; Johnston, Priscilla; Topham, Paul D.; Wang, Linge

2017-11-01

An inherent problem that restricts the practical application of superhydrophobic materials is that the superhydrophobic property is not sustainable; it can be diminished, or even lost, when the surface is physically damaged. In this work, we present an efficient approach for the fabrication of superhydrophobic fibrous fabrics with great rinse-resistance where a block copolymer has been electrospun into a nanofibrous mesh while micro-sized beads have been subsequently electrosprayed to give a morphologically composite material. The intricate nano- and microstructure of the composite was then fixed by thermally annealing the block copolymer to induce self-assembly and interdigitation of the microphase separated domains. To demonstrate this approach, a polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) nanofibrous scaffold was produced by electrospinning before SEBS beads were electrosprayed into this mesh to form a hierarchical micro/nanostructure of beads and fibers. The effects of type and density of SEBS beads on the surface morphology and wetting properties of composite membranes were studied extensively. Compared with a neat SEBS fibrous mesh, the composite membrane had enhanced hydrophobic properties. The static water contact angle increased from 139° (±3°) to 156° (±1°), while the sliding angle decreased to 8° (±1°) from nearly 90°. In order to increase the rinse-resistance of the composite membrane, a thermal annealing step was applied to physically bind the fibers and beads. Importantly, after 200 h of water flushing, the hierarchical surface structure and superhydrophobicity of the composite membrane were well retained. This work provides a new route for the creation of superhydrophobic fabrics with potential in self-cleaning applications.

All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior

DOE PAGES

Goodwin, Andrew; Wang, Weiyu; Kang, Nam -Goo; ...

2015-08-21

We present in this paper the synthesis of poly(n-butyl acrylate)-g-poly(methyl methacrylate) (PnBA-g-PMMA) multigraft copolymers via a grafting-through (macromonomer) approach. The synthesis was performed using two controlled polymerization techniques. The PMMA macromonomer was obtained by high-vacuum anionic polymerization followed by the copolymerization of n-butyl acrylate and PMMA macromonomer using reversible addition–fragmentation chain transfer (RAFT) polymerization to yield the desired all-acrylic multigraft structures. The PnBA-g-PMMA multigraft structures exhibit randomly spaced branch points with various PMMA contents, ranging from 15 to 40 vol %, allowing an investigation into how physical properties vary with differences in the number of branch points and molecular weightmore » of grafted side chains. The determination of molecular weight and polydispersity indices of both the PMMA macromonomer and the graft copolymers was carried out using size exclusion chromatography with triple detection, and the structural characteristics of both the macromonomer and PnBA-g-PMMA graft materials were characterized by 1H and 13C NMR. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was employed for monitoring the macromonomer synthesis. Thermal characteristics of the materials were analyzed using differential scanning calorimetry and thermogravimetric analysis. The mechanical performance of the graft materials was characterized by rheology and dynamic mechanical analysis, revealing that samples with PMMA content of 25–40 vol % exhibit superior elastomeric properties as compared to materials containing short PMMA side chains or <25 vol % PMMA. In conclusion, atomic force microscopy showed a varying degree of microphase separation between the glassy and rubbery components that is strongly dependent on PMMA side chain molecular weight.« less

Dynamics of aqueous binary glass-formers confined in MCM-41.

PubMed

Elamin, Khalid; Jansson, Helén; Swenson, Jan

2015-05-21

Dielectric permittivity measurements were performed on water solutions of propylene glycol (PG) and propylene glycol monomethyl ether (PGME) confined in 21 Å pores of the silica matrix MCM-41 C10 in wide frequency (10(-2)-10(6) Hz) and temperature (130-250 K) ranges. The aim was to elucidate how the formation of large hydrogen bonded structural entities, found in bulk solutions of PGME, was affected by the confined geometry, and to make comparisons with the dynamic behavior of the PG-water system. For all solutions the measurements revealed four almost concentration independent relaxation processes. The intensity of the fastest process is low compared to the other relaxation processes and might be caused by both hydroxyl groups of the pore surfaces and by local motions of water and solute molecules. The second fastest process contains contributions from both the main water relaxation as well as the intrinsic β-relaxation of the solute molecules. The third fastest process is the viscosity related α-relaxation. Its concentration independency is very different compared to the findings for the corresponding bulk systems, particularly for the PGME-water system. The experimental data suggests that the surface interactions induce a micro-phase separation of the two liquids, resulting in a full molecular layer of water molecules coordinating to the hydrophilic hydroxyl groups on the surfaces of the silica pores. This, in turn, increases the geometrical confinement effect for the remaining solution even more and prevents the building up of the same type of larger structural entities in the PGME-water system as in the corresponding bulk solutions. The slowest process is mainly hidden in the high conductivity contribution at low frequencies, but its temperature dependence can be extracted for the PGME-water system. However, its origin is not fully clear, as will be discussed.

Analysis of airfoil leading edge separation bubbles

NASA Technical Reports Server (NTRS)

Carter, J. E.; Vatsa, V. N.

1982-01-01

A local inviscid-viscous interaction technique was developed for the analysis of low speed airfoil leading edge transitional separation bubbles. In this analysis an inverse boundary layer finite difference analysis is solved iteratively with a Cauchy integral representation of the inviscid flow which is assumed to be a linear perturbation to a known global viscous airfoil analysis. Favorable comparisons with data indicate the overall validity of the present localized interaction approach. In addition numerical tests were performed to test the sensitivity of the computed results to the mesh size, limits on the Cauchy integral, and the location of the transition region.

Interaction of viscous and inviscid instability modes in separation-bubble transition

NASA Astrophysics Data System (ADS)

Brinkerhoff, Joshua R.; Yaras, Metin I.

2011-12-01

This paper describes numerical simulations that are used to examine the interaction of viscous and inviscid instability modes in laminar-to-turbulent transition in a separation bubble. The results of a direct numerical simulation are presented in which separation of a laminar boundary-layer occurs in the presence of an adverse streamwise pressure gradient. The simulation is performed at low freestream-turbulence levels and at a flow Reynolds number and pressure distribution approximating those typically encountered on the suction side of low-pressure turbine blades in a gas-turbine engine. The simulation results reveal the development of a viscous instability upstream of the point of separation which produces streamwise-oriented vortices in the attached laminar boundary layer. These vortices remain embedded in the flow downstream of separation and are carried into the separated shear layer, where they are amplified by the local adverse pressure-gradient and contribute to the formation of coherent hairpin-like vortices. A strong interaction is observed between these vortices and the inviscid instability that typically dominates the shear layer in the separated zone. The interaction is noted to determine the spanwise extent of the vortical flow structures that periodically shed from the downstream end of the separated shear layer. The structure of the shed vortical flow structures is examined and compared with the coherent structures typically observed within turbulent boundary layers.

Modeling stick-slip-separation dynamics in a bimodal standing wave ultrasonic motor

NASA Astrophysics Data System (ADS)

Li, Xiang; Yao, Zhiyuan; Lv, Qibao; Liu, Zhen

2016-11-01

Ultrasonic motor (USM) is an electromechanical coupling system with ultrasonic vibration, which is driven by the frictional contact force between the stator (vibrating body) and the rotor/slider (driven body). Stick-slip motion can occur at the contact interface when USM is operating, which may affect the performance of the motor. This paper develops a physically-based model to investigate the complex stick-slip-separation dynamics in a bimodal standing wave ultrasonic motor. The model includes both friction nonlinearity and intermittent separation nonlinearity of the system. Utilizing Hamilton's principle and assumed mode method, the dynamic equations of the stator are deduced. Based on the dynamics of the stator and the slider, sticking force during the stick phase is derived, which is used to examine the stick-to-slip transition. Furthermore, the stick-slip-separation kinematics is analyzed by establishing analytical criteria that predict the transition between stick, slip and separation of the interface. Stick-slip-separation motion is observed in the resulting model, and numerical simulations are performed to study the influence of parameters on the range of possible motions. Results show that stick-slip motion can occur with greater preload and smaller voltage amplitude. Furthermore, a dimensionless parameter is proposed to predict the occurrence of stick-slip versus slip-separation motions, and its role in designing ultrasonic motors is discussed. It is shown that slip-separation motion is favorable for the slider velocity.

A Longitudinal Study of Adolescent Adjustment Following Family Transitions

ERIC Educational Resources Information Center

Ruschena, Eda; Prior, Margot; Sanson, Ann; Smart, Diana

2005-01-01

Background: This study examined the impact of family transitions, that is, parental separation, divorce, remarriage and death, upon the lives of Australian children and adolescents in a longitudinal study of temperament and development. Methods: Using longitudinal and concurrent questionnaire data, outcomes for young people experiencing…

Automated transit networks (ATN) : a review of the state of the industry and prospects for the future.

DOT National Transportation Integrated Search

2014-09-01

The concept of Automated Transit Networks (ATN) - in which fully automated vehicles on exclusive, grade-separated guideways : provide on-demand, primarily non-stop, origin-to-destination service over an area network has been around since the 1950...

Large impact of reorganization energy on photovoltaic conversion due to interfacial charge-transfer transitions.

PubMed

Fujisawa, Jun-ichi

2015-05-14

Interfacial charge-transfer (ICT) transitions are expected to be a novel charge-separation mechanism for efficient photovoltaic conversion featuring one-step charge separation without energy loss. Photovoltaic conversion due to ICT transitions has been investigated using several TiO2-organic hybrid materials that show organic-to-inorganic ICT transitions in the visible region. In applications of ICT transitions to photovoltaic conversion, there is a significant problem that rapid carrier recombination is caused by organic-inorganic electronic coupling that is necessary for the ICT transitions. In order to solve this problem, in this work, I have theoretically studied light-to-current conversions due to the ICT transitions on the basis of the Marcus theory with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. An apparent correlation between the reported incident photon-to-current conversion efficiencies (IPCE) and calculated reorganization energies was clearly found, in which the IPCE increases with decreasing the reorganization energy consistent with the Marcus theory in the inverted region. This activation-energy dependence was systematically explained by the equation formulated by the Marcus theory based on a simple excited-state kinetic scheme. This result indicates that the reduction of the reorganization energy can suppress the carrier recombination and enhance the IPCE. The reorganization energy is predominantly governed by the structural change in the chemical-adsorption moiety between the ground and ICT excited states. This work provides crucial knowledge for efficient photovoltaic conversion due to ICT transitions.

Electrically detected crystal orientation dependent spin-Rabi beat oscillation of c-Si(111)/SiO2 interface states

NASA Astrophysics Data System (ADS)

Paik, Seoyoung; Lee, Sang-Yun; McCamey, Dane R.; Boehme, Christoph

2011-12-01

Electrically detected spin-Rabi beat oscillation of pairs of paramagnetic near interface states at the phosphorous doped (1016 cm-3) Si(111)/SiO2 interface is reported. Due to the g-factor anisotropy of the Pb center (a silicon surface dangling bond), one can tune intrapair Larmor frequency differences (Larmor separations) by orientation of the crystal with regard to an external magnetic field. Since Larmor separation governs the number of beating spin pairs, crystal orientation can control the beat current. This is used to identify spin states that are paired by mutual electronic transitions. The experiments confirm the presence of the previously reported 31P-Pb transition and provide direct experimental evidence of the previously hypothesized Pb-E' center (a near interface SiO2 bulk state) transition.

Casimir quantum levitation tuned by means of material properties and geometries

NASA Astrophysics Data System (ADS)

Dou, Maofeng; Lou, Fei; Boström, Mathias; Brevik, Iver; Persson, Clas

2014-05-01

The Casimir force between two surfaces is attractive in most cases. Although stable suspension of nano-objects has been achieved, the sophisticated geometries make them difficult to be merged with well-established thin film processes. We find that by introducing thin film surface coating on porous substrates, a repulsive to attractive force transition is achieved when the separations are increased in planar geometries, resulting in a stable suspension of two surfaces near the force transition separation. Both the magnitude of the force and the transition distance can be flexibly tailored though modifying the properties of the considered materials, that is, thin film thickness, doping concentration, and porosity. This stable suspension can be used to design new nanodevices with ultralow friction. Moreover, it might be convenient to merge this thin film coating approach with micro- and nanofabrication processes in the future.

Fathering After Marital Separation

ERIC Educational Resources Information Center

Keshet, Harry Finkelstein; Rosenthal, Kristine M.

1978-01-01

Deals with experiences of a group of separated or divorced fathers who chose to remain fully involved in the upbringing of their children. As they underwent transition from married parenthood to single fatherhood, these men learned that meeting demands of child care contributed to personal stability and growth. (Author)

Structural and phase transitions of one and two polymer mushrooms in poor solvent

NASA Astrophysics Data System (ADS)

Yang, Delian; Wang, Qiang

2014-05-01

Using the recently proposed fast lattice Monte Carlo (FLMC) simulations and the corresponding lattice self-consistent field (LSCF) calculations based on the same model system, where multiple occupancy of lattice sites is allowed [Q. Wang, Soft Matter 5, 4564 (2009); Q. Wang, Soft Matter 5, 6206 (2010)], we studied the coil-globule transition (CGT) of one-mushroom systems and the fused-separated transition (FST) of two-mushroom systems, where a polymer mushroom is formed by a group of n homopolymer chains each of N segments end-grafted at the same point onto a flat substrate and immersed in a poor solvent. With our soft potential that allows complete particle overlapping, LSCF theory neglecting the system fluctuations/correlations becomes exact in the limit of n → ∞, and FLMC results approach LSCF predictions with increasing n. Using LSCF calculations, we systematically constructed the phase diagrams of one- and two-mushroom systems. A second-order symmetric-asymmetric transition (SAT) was found in the globule state of one-mushroom systems, where the rotational symmetry around the substrate normal passing through the grafting point is broken in each individual configuration but preserved by the degeneracy of different orientations of these asymmetric configurations. Three different states were also found in two-mushroom systems: separated coils, separated globules, and fused globule. We further studied the coupling between FST in two-mushroom systems and CGT and SAT of each mushroom. Finally, direct comparisons between our simulation and theoretical results, without any parameter-fitting, unambiguously and quantitatively revealed the fluctuation/correlation effects on these phase transitions.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

Military Transition Assistance Program (TAP): An Overview

DTIC Science & Technology

2017-03-15

Title II of P.L. 112-56) which made a pre-separation counseling program mandatory for all servicemembers who have served at least 180 continuous days...anticipated retirement date or 12-month period preceding the anticipated separation date. It also specifies that pre-separation counseling should...in the development, management oversight, and strategic planning of TAP. TAP Counseling Requirements Over time, Congress has increased the

Atomic Force Microscopy Studies of Functional and Dysfunctional Pulmonary Surfactant Films. I. Micro- and Nanostructures of Functional Pulmonary Surfactant Films and the Effect of SP-A

PubMed Central

Zuo, Yi Y.; Keating, Eleonora; Zhao, Lin; Tadayyon, Seyed M.; Veldhuizen, Ruud A. W.; Petersen, Nils O.; Possmayer, Fred

2008-01-01

Monolayers of a functional pulmonary surfactant (PS) can reach very low surface tensions well below their equilibrium value. The mechanism by which PS monolayers reach such low surface tensions and maintain film stability remains unknown. As shown previously by fluorescence microscopy, phospholipid phase transition and separation seem to be important for the normal biophysical properties of PS. This work studied phospholipid phase transitions and separations in monolayers of bovine lipid extract surfactant using atomic force microscopy. Atomic force microscopy showed phospholipid phase separation on film compression and a monolayer-to-multilayer transition at surface pressure 40–50 mN/m. The tilted-condensed phase consisted of domains not only on the micrometer scale, as detected previously by fluorescence microscopy, but also on the nanometer scale, which is below the resolution limits of conventional optical methods. The nanodomains were embedded uniformly within the liquid-expanded phase. On compression, the microdomains broke up into nanodomains, thereby appearing to contribute to tilted-condensed and liquid-expanded phase remixing. Addition of surfactant protein A altered primarily the nanodomains and promoted the formation of multilayers. We conclude that the nanodomains play a predominant role in affecting the biophysical properties of PS monolayers and the monolayer-to-multilayer transition. PMID:18212010

Dehydration induced phase transitions in a microfluidic droplet array for the separation of biomolecules

NASA Astrophysics Data System (ADS)

Nelson, Chris; Anna, Shelley

2013-11-01

Droplet-based strategies for fluid manipulation have seen significant application in microfluidics due to their ability to compartmentalize solutions and facilitate highly parallelized reactions. Functioning as micro-scale reaction vessels, droplets have been used to study protein crystallization, enzyme kinetics, and to encapsulate whole cells. Recently, the mass transport out of droplets has been used to concentrate solutions and induce phase transitions. Here, we show that droplets trapped in a microfluidic array will spontaneously dehydrate over the course of several hours. By loading these devices with an initially dilute aqueous polymer solution, we use this slow dehydration to observe phase transitions and the evolution of droplet morphology in hundreds of droplets simultaneously. As an example, we trap and dehydrate droplets of a model aqueous two-phase system consisting of polyethylene glycol and dextran. Initially the drops are homogenous, then after some time the polymer concentration reaches a critical point and two phases form. As water continues to leave the system, the drops transition from a microemulsion of DEX in PEG to a core-shell configuration. Eventually, changes in interfacial tension, driven by dehydration, cause the DEX core to completely de-wet from the PEG shell. Since aqueous two phase systems are able to selectively separate a variety of biomolecules, this core shedding behavior has the potential to provide selective, on-chip separation and concentration.

The mechanics of pressed-pellet separators in molten salt batteries

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

Long, Kevin Nicholas; Roberts, Christine Cardinal; Roberts, Scott Alan

2014-06-01

We present a phenomenological constitutive model that describes the macroscopic behavior of pressed-pellet materials used in molten salt batteries. Such materials include separators, cathodes, and anodes. The purpose of this model is to describe the inelastic deformation associated with the melting of a key constituent, the electrolyte. At room temperature, all constituents of these materials are solid and do not transport cations so that the battery is inert. As the battery is heated, the electrolyte, a constituent typically present in the separator and cathode, melts and conducts charge by flowing through the solid skeletons of the anode, cathode, and separator.more » The electrochemical circuit is closed in this hot state of the battery. The focus of this report is on the thermal-mechanical behavior of the separator, which typically exhibits the most deformation of the three pellets during the process of activating a molten salt battery. Separator materials are composed of a compressed mixture of a powdered electrolyte, an inert binder phase, and void space. When the electrolyte melts, macroscopically one observes both a change in volume and shape of the separator that depends on the applied boundary conditions during the melt transition. Although porous flow plays a critical role in the battery mechanics and electrochemistry, the focus of this report is on separator behavior under flow-free conditions in which the total mass of electrolyte is static within the pellet. Specific poromechanics effects such as capillary pressure, pressure-saturation, and electrolyte transport between layers are not considered. Instead, a phenomenological model is presented to describe all such behaviors including the melting transition of the electrolyte, loss of void space, and isochoric plasticity associated with the binder phase rearrangement. The model is appropriate for use finite element analysis under finite deformation and finite temperature change conditions. The model reasonably describes the stress dependent volume and shape change associated with dead load compression and spring-type boundary conditions; the latter is relevant in molten salt batteries. Future work will transition the model towards describing the solid skeleton of the separator in the traditional poromechanics context.« less

50 CFR 14.123 - Care in transit.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Wild Mammals and Birds to the United States Specifications for Nonhuman Primates § 14.123 Care in transit. (a) A primate shall be observed for signs of distress and given food and water according to the... to keep enclosures containing primates sufficiently separated in the conveyance or holding area to...

50 CFR 14.123 - Care in transit.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Wild Mammals and Birds to the United States Specifications for Nonhuman Primates § 14.123 Care in transit. (a) A primate shall be observed for signs of distress and given food and water according to the... to keep enclosures containing primates sufficiently separated in the conveyance or holding area to...

Nanoscale ferromagnetism in phase-separated manganites

NASA Astrophysics Data System (ADS)

Mori, S.; Horibe, Y.; Asaka, T.; Matsui, Y.; Chen, C. H.; Cheong, S. W.

2007-03-01

Magnetic domain structures in phase-separated manganites were investigated by low-temperature Lorentz electron microscopy, in order to understand some unusual physical properties such as a colossal magnetoresistance (CMR) effect and a metal-to-insulator transition. In particular, we examined a spatial distribution of the charge/orbital-ordered (CO/OO) insulator state and the ferromagnetic (FM) metallic one in phase-separated manganites; Cr-doped Nd0.5Ca0.5MnO3 and ( La1-xPrx)CaMnO3 with x=0.375, by obtaining both the dark-field images and Lorentz electron microscopic ones. It is found that an unusual coexistence of the CO/OO and FM metallic states below a FM transition temperature in the two compounds. The present experimental results clearly demonstrated the coexisting state of the two distinct ground states in manganites.

Nonequilibrium Phase Transition in a Model for Social Influence

NASA Astrophysics Data System (ADS)

Castellano, Claudio; Marsili, Matteo; Vespignani, Alessandro

2000-10-01

We present extensive numerical simulations of the Axelrod's model for social influence, aimed at understanding the formation of cultural domains. This is a nonequilibrium model with short range interactions and a remarkably rich dynamical behavior. We study the phase diagram of the model and uncover a nonequilibrium phase transition separating an ordered (culturally polarized) phase from a disordered (culturally fragmented) one. The nature of the phase transition can be continuous or discontinuous depending on the model parameters. At the transition, the size of cultural regions is power-law distributed.

Strategic Forum Number 208: Turbulent Transition in Iraq: Can It Succeed?

DTIC Science & Technology

2004-06-01

ministers including a prime minister, and a judiciary. There is separation of powers —legislative, executive, and judicial. The assembly will elect the... separation of powers based on geographic and historical realities and not race, ethnicity, nationality, or religious sect (confession). Formulation of

Enzymatic Transition States, Transition-State Analogs, Dynamics, Thermodynamics, and Lifetimes

PubMed Central

Schramm, Vern L.

2017-01-01

Experimental analysis of enzymatic transition-state structures uses kinetic isotope effects (KIEs) to report on bonding and geometry differences between reactants and the transition state. Computational correlation of experimental values with chemical models permits three-dimensional geometric and electrostatic assignment of transition states formed at enzymatic catalytic sites. The combination of experimental and computational access to transition-state information permits (a) the design of transition-state analogs as powerful enzymatic inhibitors, (b) exploration of protein features linked to transition-state structure, (c) analysis of ensemble atomic motions involved in achieving the transition state, (d) transition-state lifetimes, and (e) separation of ground-state (Michaelis complexes) from transition-state effects. Transition-state analogs with picomolar dissociation constants have been achieved for several enzymatic targets. Transition states of closely related isozymes indicate that the protein’s dynamic architecture is linked to transition-state structure. Fast dynamic motions in catalytic sites are linked to transition-state generation. Enzymatic transition states have lifetimes of femtoseconds, the lifetime of bond vibrations. Binding isotope effects (BIEs) reveal relative reactant and transition-state analog binding distortion for comparison with actual transition states. PMID:21675920

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, C.A.; Worden, E.F.

1995-08-22

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of {sup 167}Er. The hyperfine structure of {sup 167}Er was used to find two three-step photoionization pathways having a common upper energy level. 3 figs.

Impact of L/D on 90 Degree Sharp-Edge Orifice Flow with Manifold Passage Cross Flow (Preprint)

DTIC Science & Technology

2007-04-30

that are observed by measurement as the flow transitions from non-cavitation to cavitation (turbulent flow), supercavitation , and finally separation in...include inception of cavitation, supercavitation , and separation. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF...cavitation to cavitation (turbulent flow), supercavitation , and finally separation in sharp-edge 90 degree orifices. This study includes orifice L/D from

Monte Carlo simulations of magnetic properties of Kekulene structure bilayers separate by a nonmagnetic with RKKY interactions

NASA Astrophysics Data System (ADS)

Jabar, A.; Masrour, R.

2018-05-01

The magnetic properties of magnetic bilayers of Kekulene structure separate by a nonmagnetic layer with Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange interactions with Ising spin model have been studied using Monte Carlo simulations. The RKKY interaction between the bilayers of Kekulene is considered for different distances. The transition temperature has been deduced from the magnetizations and magnetic susceptibilities partial for a fixed value of nonmagnetic layer. The reduced transition temperatures are also deduced from the total magnetization and total magnetic susceptibilities with different values of L. The magnetic hysteresis cycles of systems have been determined.

A new method for separating first row transition metals and actinides from synthetic melt glass

DOE PAGES

Roman, Audrey Rae; Bond, Evelyn M.

2016-01-14

A new method was developed for separating Co, Fe, and Sc from complex debris matrices using the extraction chromatography resin DGA. The activation products Co-58, Mn-54, and Sc-46 were used to characterize the separation of the synthetic melt glass solutions. In the separation scheme that was developed, Au, Co, Cu, Fe, Sc, and Ti were separated from the rest of the sample constituents. In this paper, the synthetic melt glass separation method, efficiency, recoveries, and the length of procedure will be discussed. In conclusion, batch contact adsorption studies for Na and Sc for DGA resin are discussed as well.

Turbulent Transition in Iraq: Can It Succeed? (Strategic Forum, Number 208, June 2004)

DTIC Science & Technology

2004-06-01

council, a council of ministers including a prime minister, and a judiciary. There is separation of powers —legislative, executive, and judicial. The...defined as a system of separation of powers based on geographic and historical realities and not race, ethnicity, nationality, or religious sect

The Archetype of Initiation in Selected Novels of Black Adolescence.

ERIC Educational Resources Information Center

Pettigrew, B. Joye

1972-01-01

This paper discusses several novels written by black American writers that deal with the initiation experiences of young blacks, and should, therefore, appeal to black adolescents. The novels are grouped according to the three stages in the initiation experience of the adolescent: separation; transition; and incorporation. In separation, the…

Experimental Investigation of Transition to Turbulence as Affected By Passing Wakes

NASA Technical Reports Server (NTRS)

Kaszeta, Richard W.; Ashpis, David E.; Simon, Terrence W.

2001-01-01

This paper presents experimental results from a study of the effects of periodically passing wakes upon laminar-to-turbulent transition and separation in a low-pressure turbine passage. The test section geometry is designed to simulate unsteady wakes in turbine engines for studying their effects on boundary layers and separated flow regions over the suction surface by using a single suction surface and a single pressure surface to simulate a single turbine blade passage. Single-wire, thermal anemometry techniques are used to measure time-resolved and phase averaged, wall-normal profiles of velocity, turbulence intensity and intermittency at multiple streamwise locations over the turbine airfoil suction surface. These data are compared to steady-state wake-free data collected in the same geometry to identify the effects of wakes upon laminar-to-turbulent transition. Results are presented for flows with a Reynolds number based on suction surface length and stage exit velocity of 50,000 and an approach flow turbulence intensity of 2.5%. While both existing design and experimental data are primarily concerned with higher Reynolds number flows (Re greater than 100,000), recent advances in gas turbine engines, and the accompanying increase in laminar and transitional flow effects, have made low-Re research increasingly important. From the presented data, the effects of passing wakes on transition and separation in the boundary layer, due to both increased turbulence levels and varying streamwise pressure gradients are presented. The results show how the wakes affect transition. The wakes affect the flow by virtue of their difference in turbulence levels and scales from those of the free-stream and by virtue of their ensemble- averaged velocity deficits, relative to the free-stream velocity, and the concomitant changes in angle of attack and temporal pressure gradients. The relationships between the velocity oscillations in the freestream and the unsteady velocity profile shapes in the near-wall flow are described. In this discussion is support for the theory that bypass transition is a response of the near-wall viscous layer to pressure fluctuations imposed upon it from the free-stream flow. Recent transition models are based on that premise. The data also show a significant lag between when the wake is present over the surface and when transition begins.cous layer to pressure fluctuations imposed upon it from the free-stream flow. Recent transition models are based on that premise. The data also show a significant lag between when the wake is present over the surface and when transition begins.cous layer to pressure fluctuations imposed upon it from the free-stream flow. Recent transition models are based on that premise. The data also show a significant lag between when the wake is present over the surface and when transition begins.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

PubMed

Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-21

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Interface and phase transition between Moore-Read and Halperin 331 fractional quantum Hall states: Realization of chiral Majorana fermion

NASA Astrophysics Data System (ADS)

Yang, Kun

2017-12-01

We consider an interface separating the Moore-Read state and Halperin 331 state in a half-filled Landau level, which can be realized in a double quantum well system with varying interwell tunneling and/or interaction strengths. In the presence of electron tunneling and strong Coulomb interactions across the interface, we find that all charge modes localize and the only propagating mode left is a chiral Majorana fermion mode. Methods to probe this neutral mode are proposed. A quantum phase transition between the Moore-Read and Halperin 331 states is described by a network of such Majorana fermion modes. In addition to a direct transition, they may also be separated by a phase in which the Majorana fermions are delocalized, realizing an incompressible state which exhibits quantum Hall charge transport and bulk heat conduction.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

NASA Astrophysics Data System (ADS)

Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-01

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Recent Progress on Transition Metal Catalyst Separation and Recycling in ATRP.

PubMed

Ding, Mingqiang; Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2015-10-01

Atom transfer radical polymerization (ATRP) is a versatile and robust tool to synthesize a wide spectrum of monomers with various designable structures. However, it usually needs large amounts of transition metal as the catalyst to mediate the equilibrium between the dormant and propagating species. Unfortunately, the catalyst residue may contaminate or color the resultant polymers, which limits its application, especially in biomedical and electronic materials. How to efficiently and economically remove or reduce the catalyst residue from its products is a challenging and encouraging task. Herein, recent advances in catalyst separation and recycling are highlighted with a focus on (1) highly active ppm level transition metal or metal free catalyzed ATRP; (2) post-purification method; (3) various soluble, insoluble, immobilized/soluble, and reversible supported catalyst systems; and (4) liquid-liquid biphasic catalyzed systems, especially thermo-regulated catalysis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An evaluation of three two-dimensional computational fluid dynamics codes including low Reynolds numbers and transonic Mach numbers

NASA Technical Reports Server (NTRS)

Hicks, Raymond M.; Cliff, Susan E.

1991-01-01

Full-potential, Euler, and Navier-Stokes computational fluid dynamics (CFD) codes were evaluated for use in analyzing the flow field about airfoils sections operating at Mach numbers from 0.20 to 0.60 and Reynolds numbers from 500,000 to 2,000,000. The potential code (LBAUER) includes weakly coupled integral boundary layer equations for laminar and turbulent flow with simple transition and separation models. The Navier-Stokes code (ARC2D) uses the thin-layer formulation of the Reynolds-averaged equations with an algebraic turbulence model. The Euler code (ISES) includes strongly coupled integral boundary layer equations and advanced transition and separation calculations with the capability to model laminar separation bubbles and limited zones of turbulent separation. The best experiment/CFD correlation was obtained with the Euler code because its boundary layer equations model the physics of the flow better than the other two codes. An unusual reversal of boundary layer separation with increasing angle of attack, following initial shock formation on the upper surface of the airfoil, was found in the experiment data. This phenomenon was not predicted by the CFD codes evaluated.

Externalizing Behaviour and Academic Performance--The Cross-Lagged Relationship during School Transition

ERIC Educational Resources Information Center

Palmu, Iines R.; Närhi, Vesa M.; Savolainen, Hannu K.

2018-01-01

The current study examined the over-time association between externalizing behaviour problems and academic performance during school transition in a cross-lagged design. The main focus was to reveal whether the externalizing behaviour composite and its components separately, including symptoms of CD and ADHD, differ in their relationship with…

Better Parents, More Stable Partners: Union Transitions among Cohabiting Parents

ERIC Educational Resources Information Center

McClain, Lauren Rinelli

2011-01-01

Data from the Fragile Families and Child Wellbeing Study (N = 1,702 couples) are employed to examine the association between mother- and father-reported parenting characteristics (father involvement and coparenting) and transitions out of cohabitation through marriage or separation in the 5 years after a child is born. Father involvement and…

Volume-wise destruction of the antiferromagnetic Mott insulating state through quantum tuning

DOE PAGES

B. A. Frandsen; Liu, L.; Cheung, S. C.; ...

2016-08-17

RENiO 3 (RE=rare-earth element) and V 2O 3 are archetypal Mott insulator systems. When tuned by chemical substitution (RENiO 3) or pressure (V 2O 3), they exhibit a quantum phase transition (QPT) between an antiferromagnetic Mott insulating state and a paramagnetic metallic state. Because novel physics often appears near a Mott QPT, the details of this transition, such as whether it is first or second order, are important. Here, we demonstrate through muon spin relaxation/rotation (μSR) experiments that the QPT in RENiO 3 and V 2O 3 is first order: the magnetically ordered volume fraction decreases to zero at themore » QPT, resulting in a broad region of intrinsic phase separation, while the ordered magnetic moment retains its full value until it is suddenly destroyed at the QPT. These findings bring to light a surprising universality of the pressure-driven Mott transition, revealing the importance of phase separation and calling for further investigation into the nature of quantum fluctuations underlying the transition.« less

Transit timing variations for planets co-orbiting in the horseshoe regime

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

Vokrouhlický, David; Nesvorný, David, E-mail: vokrouhl@cesnet.cz, E-mail: davidn@boulder.swri.edu

2014-08-10

Although not yet detected, pairs of exoplanets in 1:1 mean motion resonance probably exist. Low eccentricity, near-planar orbits, which in the comoving frame follow horseshoe trajectories, are one of the possible stable configurations. Here we study transit timing variations (TTVs) produced by mutual gravitational interaction of planets in this orbital architecture, with the goal to develop methods that can be used to recognize this case in observational data. In particular, we use a semi-analytic model to derive parametric constraints that should facilitate data analysis. We show that characteristic traits of the TTVs can directly constrain the (1) ratio of planetarymore » masses and (2) their total mass (divided by that of the central star) as a function of the minimum angular separation as seen from the star. In an ideal case, when transits of both planets are observed and well characterized, the minimum angular separation can also be inferred from the data. As a result, parameters derived from the observed transit timing series alone can directly provide both planetary masses scaled to the central star mass.« less

Volume-wise destruction of the antiferromagnetic Mott insulating state through quantum tuning

PubMed Central

Frandsen, Benjamin A.; Liu, Lian; Cheung, Sky C.; Guguchia, Zurab; Khasanov, Rustem; Morenzoni, Elvezio; Munsie, Timothy J. S.; Hallas, Alannah M.; Wilson, Murray N.; Cai, Yipeng; Luke, Graeme M.; Chen, Bijuan; Li, Wenmin; Jin, Changqing; Ding, Cui; Guo, Shengli; Ning, Fanlong; Ito, Takashi U.; Higemoto, Wataru; Billinge, Simon J. L.; Sakamoto, Shoya; Fujimori, Atsushi; Murakami, Taito; Kageyama, Hiroshi; Alonso, Jose Antonio; Kotliar, Gabriel; Imada, Masatoshi; Uemura, Yasutomo J.

2016-01-01

RENiO3 (RE=rare-earth element) and V2O3 are archetypal Mott insulator systems. When tuned by chemical substitution (RENiO3) or pressure (V2O3), they exhibit a quantum phase transition (QPT) between an antiferromagnetic Mott insulating state and a paramagnetic metallic state. Because novel physics often appears near a Mott QPT, the details of this transition, such as whether it is first or second order, are important. Here, we demonstrate through muon spin relaxation/rotation (μSR) experiments that the QPT in RENiO3 and V2O3 is first order: the magnetically ordered volume fraction decreases to zero at the QPT, resulting in a broad region of intrinsic phase separation, while the ordered magnetic moment retains its full value until it is suddenly destroyed at the QPT. These findings bring to light a surprising universality of the pressure-driven Mott transition, revealing the importance of phase separation and calling for further investigation into the nature of quantum fluctuations underlying the transition. PMID:27531192

Long Range In-Plane Order of Oriented Diblock Copolymer Thin Films by Graphoepitaxy

NASA Astrophysics Data System (ADS)

Fontana, Scott; Dadmun, Mark; Lowndes, Douglas

2003-03-01

Previous work by Russell and coworkers has demonstrated that controlling the interfacial energies and wetting behavior of an asymmetric diblock copolymer enables the control of the orientation of its microphases. In particular the cylindrical phase can be readily aligned perpendicular to a substrate when it is placed on a surface that is neutral to both components of the copolymer. The minor phase, PMMA may then be removed using UV radiation leaving a nanoporous template. In this work, we will report long range, in-plane ordering of the hexagonally packed nanopores that is achieved using graphoepitaxy. The long range ordered and vertically aligned diblock copolymer film can be used to produce arrays of catalytic nickel dots, which grow vertically aligned carbon nano-fibers (VACNF), resulting in a well ordered array of VACNFs.

KIC 12557548 and Similar Stars as SETI Targets

NASA Astrophysics Data System (ADS)

Star Cartier, Kimberly Michelle

2015-01-01

This project aims to construct a robust information theoretic metric to quantify anomalous transit light curves and compare regular and irregular transits in a reproducible way. Using this metric we can distinguish natural transits from predicted extraterrestrial intelligence (ETI) communication that utilizes transiting mega-structures to alter the transit shape and depth in a measurable way. KIC-12557548b (KIC-1255b) is such an anomalous planet, with highly variable consecutive transit depths and shapes that have been explained by Rappaport et al. (2012) and Croll et al. (2014) as due to a disintegrating sub-Mercury sized planet with a debris tail encompassing the planetary orbit. However, Arnold (2005) and later Forgan (2013) presented models showing that planet-sized, non-circular artificial structures transiting their host star could be identified as non-natural by light curves anomalous in their duration and asymmetry, as in the case of KIC-1255b. If such mega-engineering structures were able to alter their aspects on orbital timescales, the resulting transit depths could be used to transmit information at low bandwidth. We use KIC-1255b as a benchmark case for separating anomalous transit signals that resemble ETI predictions but are naturally occurring. To do this, we use the Kullback-Leibler (KL) divergence of the KIC-1255b transit depth time series to quantify the entropy of the transit depth series. We calibrate our relative entropy metric by calculating the KL divergence of the Kepler-5b transits, which are markedly constant compared to KIC-1255b. Artificially generated transit depth time series data using Arnold's beacons allow us to calculate the KL divergence of predicted ETI communications and show that while KIC-1255b might match ETI predictions of shape and depth variations, the entropy content of the datasets are distinct by our metric. Thus we can use the entropy metric to test other cases of anomalous transits to separate out those transiting planets that can be explained through natural models and those for which an ETI hypothesis might be entertained.

Anomalous critical behavior in the polymer collapse transition of three-dimensional lattice trails.

PubMed

Bedini, Andrea; Owczarek, Aleksander L; Prellberg, Thomas

2012-07-01

Trails (bond-avoiding walks) provide an alternative lattice model of polymers to self-avoiding walks, and adding self-interaction at multiply visited sites gives a model of polymer collapse. Recently a two-dimensional model (triangular lattice) where doubly and triply visited sites are given different weights was shown to display a rich phase diagram with first- and second-order collapse separated by a multicritical point. A kinetic growth process of trails (KGTs) was conjectured to map precisely to this multicritical point. Two types of low-temperature phases, a globule phase and a maximally dense phase, were encountered. Here we investigate the collapse properties of a similar extended model of interacting lattice trails on the simple cubic lattice with separate weights for doubly and triply visited sites. Again we find first- and second-order collapse transitions dependent on the relative sizes of the doubly and triply visited energies. However, we find no evidence of a low-temperature maximally dense phase with only the globular phase in existence. Intriguingly, when the ratio of the energies is precisely that which separates the first-order from the second-order regions anomalous finite-size scaling appears. At the finite-size location of the rounded transition clear evidence exists for a first-order transition that persists in the thermodynamic limit. This location moves as the length increases, with its limit apparently at the point that maps to a KGT. However, if one fixes the temperature to sit at exactly this KGT point, then only a critical point can be deduced from the data. The resolution of this apparent contradiction lies in the breaking of crossover scaling and the difference in the shift and transition width (crossover) exponents.

Voluntary sway and rapid orthogonal transitions of voluntary sway in young adults, and low and high fall-risk older adults.

PubMed

Tucker, Murray G; Kavanagh, Justin J; Morrison, Steven; Barrett, Rod S

2009-10-01

Falls amongst older people have been linked to reduced postural stability and slowed movement responses. The objective of this study was to examine differences in postural stability and the speed of response between young adults, low fall-risk older adults, and high fall-risk older adults during voluntary postural sway movements. Twenty-five young adults (25+/-4 years), and 32 low fall-risk (74+/-5 years), and 16 high fall-risk (79+/-7 years) older adults performed voluntary sway and rapid orthogonal transitions of voluntary sway between the anterior-posterior and medial-lateral directions. Measures included reaction and movement time and the amplitudes of the centre of pressure, centre of mass, and the separation distance between the centre of pressure and centre of mass. Both fall-risk groups compared to the young had slower reaction and movement time, greater centre of pressure and/or centre of mass amplitude in the orthogonal (non-target) direction during voluntary sway, and reduced anterior-posterior and medial-lateral separation between the centre of pressure and centre of mass during voluntary sway and orthogonal transitions. High compared to low fall-risk individuals had slower reaction and movement time, increased non-target centre of mass amplitude during voluntary sway, and reduced medial-lateral centre of pressure and centre of mass separation during voluntary sway and orthogonal transitions. Age-related deterioration of postural control resulted in slower reactive responses and reduced control of the direction of body movement during voluntary sway and orthogonal transitions. Slower postural reaction and movement time and reduced medial-lateral control of the centre of mass during voluntary sway movements are associated with increased fall-risk in community-living older people.

Model-Invariant Hybrid Computations of Separated Flows for RCA Standard Test Cases

NASA Technical Reports Server (NTRS)

Woodruff, Stephen

2016-01-01

NASA's Revolutionary Computational Aerosciences (RCA) subproject has identified several smooth-body separated flows as standard test cases to emphasize the challenge these flows present for computational methods and their importance to the aerospace community. Results of computations of two of these test cases, the NASA hump and the FAITH experiment, are presented. The computations were performed with the model-invariant hybrid LES-RANS formulation, implemented in the NASA code VULCAN-CFD. The model- invariant formulation employs gradual LES-RANS transitions and compensation for model variation to provide more accurate and efficient hybrid computations. Comparisons revealed that the LES-RANS transitions employed in these computations were sufficiently gradual that the compensating terms were unnecessary. Agreement with experiment was achieved only after reducing the turbulent viscosity to mitigate the effect of numerical dissipation. The stream-wise evolution of peak Reynolds shear stress was employed as a measure of turbulence dynamics in separated flows useful for evaluating computations.

The structure of separated flow regions occurring near the leading edge of airfoils - including transition

NASA Technical Reports Server (NTRS)

1989-01-01

Laser Doppler Velocimeter data, static pressure data, and smoke flow visualization data was obtained and analyzed to correlate with separation bubble data. The Eppler 387 airfoil was focused on at a chord Reynolds number of 100,000 and an angle of attack of 2 deg. Additional data was also obtained from the NACA 663-018 airfoil at a chord Reynolds number of 160,000 and an angle of attack of 12 deg. The structure and behavior of the transition separation bubble was documented along with the redeveloping boundary layer after reattachment over an airfoil at low Reynolds numbers. The understanding of the complex flow phenomena was examined so that analytic methods for predicting their formation and development can be improved. These analytic techniques have applications in the design and performance prediction of airfoils operating in the low Reynolds number flight regime.

Manipulating electronic phase separation in strongly correlated oxides with an ordered array of antidots

DOE PAGES

Zhang, Kai; Du, Kai; Liu, Hao; ...

2015-07-20

The interesting transport and magnetic properties in manganites depend sensitively on the nucleation and growth of electronic phase-separated domains. In this paper, by fabricating antidot arrays in La 0.325Pr 0.3Ca 0.375MnO 3 (LPCMO) epitaxial thin films, we create ordered arrays of micrometer-sized ferromagnetic metallic (FMM) rings in the LPCMO films that lead to dramatically increased metal–insulator transition temperatures and reduced resistances. The FMM rings emerge from the edges of the antidots where the lattice symmetry is broken. Based on our Monte Carlo simulation, these FMM rings assist the nucleation and growth of FMM phase domains increasing the metal–insulator transition withmore » decreasing temperature or increasing magnetic field. Finally, this study points to a way in which electronic phase separation in manganites can be artificially controlled without changing chemical composition or applying external field.« less

The Role of RNA in Biological Phase Separations.

PubMed

Fay, Marta M; Anderson, Paul J

2018-05-10

Phase transitions that alter the physical state of ribonucleoprotein particles contribute to the spacial and temporal organization of the densely packed intracellular environment. This allows cells to organize biologically coupled processes as well as respond to environmental stimuli. RNA plays a key role in phase separation events that modulate various aspects of RNA metabolism. Here, we review the role that RNA plays in ribonucleoprotein phase separations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Morphologies of precise polyethylene-based acid copolymers and ionomers

NASA Astrophysics Data System (ADS)

Buitrago, C. Francisco

Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been identified for precise acid copolymers and ionomers at room temperature: (1) liquid-like order of aggregates dispersed throughout an amorphous PE matrix, (2) one-dimensional long-range order of aggregates in layers coexisting with PE crystals, and (3) three-dimensional periodicity of aggregates in cubic lattices in a PE matrix featuring defective packing. The liquid-like morphology is a result of high content of acid or ionic substituents deterring PE crystallinity due to steric hindrance. The layered morphology occurs when the content of pendants is low and the PE segments are long enough to crystallize. The cubic morphologies occur in precise copolymers with geminal substitution of phosphonic acid (PA) groups and long, flexible PE segments. At temperatures above the thermal transitions of the PE matrix, all but one material present a liquid-like morphology. Those conditions are ideal to study the evolution of the interaggregate spacing (d*) in X-ray scattering as a function of PE segment length between pendants, pendant type and pendant architecture (specifically, mono or geminal substitution). Also at elevated temperatures, the morphologies of precise acrylic acid (AA) copolymers and ionomers were investigated further via atomistic molecular dynamics (MD) simulations. The simulations complement X-ray scattering by providing real space visualization of the aggregates, demonstrating the occurrence of isolated, string-like and even percolated aggregate structures. This is the first dissertation completely devoted to the morphology of precise acid copolymers and precise ionomers. The complete analysis of the morphologies in these novel materials provides new insights into the shapes of aggregates in acid copolymers and ionomers in general. A key aspect of this thesis is the complementary use of experimental and simulation methods to unlock a wealth of new understanding.

Toddlers' Emotional Reactions to Separation from Their Primary Caregivers: Successful Home--School Transition

ERIC Educational Resources Information Center

Xu, Yaoying

2006-01-01

The purpose of this study was to examine toddlers' emotional reactions to separation from their primary caregivers through the observation on a group of toddlers (18-30 months old) at a university preschool classroom. Interactional ethnography with ethnographic perspective and sociolinguistic discourse analysis was used as the theoretical…

Enhancing Infant-Toddler Adjustment during Transitions to Child Care: A Screening and Intervention Tool for Practitioners

ERIC Educational Resources Information Center

Fernandez, Mari T.; Marfo, Kofi

2005-01-01

Children's successful adjustment to child care involves effectively managing their separation from parents. Persistent problems with separation interfere with other relationships and with learning opportunities. The authors of this article developed a tool that caregivers can use to identify adjustment difficulties in young children who are …

Co-Sleeping and the Importation of Picture Books about Bedtime

ERIC Educational Resources Information Center

Chou, Wan-Hsiang

2009-01-01

In mainstream Western cultures where bedtime means isolation and separation from adults, picture books about bedtime are cultural artifacts created especially for this transitional process of separation. In a culture such as Taiwan where children often sleep with their parents, siblings, or other caregivers until elementary school, the need for…

Direct Observations of a Dynamically Driven Phase Transition with in situ X-Ray Diffraction in a Simple Ionic Crystal

NASA Astrophysics Data System (ADS)

Kalita, Patricia; Specht, Paul; Root, Seth; Sinclair, Nicholas; Schuman, Adam; White, Melanie; Cornelius, Andrew L.; Smith, Jesse; Sinogeikin, Stanislav

2017-12-01

We report real-time observations of a phase transition in the ionic solid CaF2 , a model A B2 structure in high-pressure physics. Synchrotron x-ray diffraction coupled with dynamic loading to 27.7 GPa, and separately with static compression, follows, in situ, the fluorite to cotunnite structural phase transition, both on nanosecond and on minute time scales. Using Rietveld refinement techniques, we examine the kinetics and hysteresis of the transition. Our results give insight into the kinetic time scale of the fluorite-cotunnite phase transition under shock compression, which is relevant to a number of isomorphic compounds.

Characteristics of the Mott transition and electronic states of high-temperature cuprate superconductors from the perspective of the Hubbard model

NASA Astrophysics Data System (ADS)

Kohno, Masanori

2018-04-01

A fundamental issue of the Mott transition is how electrons behaving as single particles carrying spin and charge in a metal change into those exhibiting separated spin and charge excitations (low-energy spin excitation and high-energy charge excitation) in a Mott insulator. This issue has attracted considerable attention particularly in relation to high-temperature cuprate superconductors, which exhibit electronic states near the Mott transition that are difficult to explain in conventional pictures. Here, from a new viewpoint of the Mott transition based on analyses of the Hubbard model, we review anomalous features observed in high-temperature cuprate superconductors near the Mott transition.

The use of total simulator training in transitioning air-carrier pilots: A field evaluation

NASA Technical Reports Server (NTRS)

Randle, R. J., Jr.; Tanner, T. A.; Hamerman, J. A.; Showalter, T. H.

1981-01-01

A field study was conducted in which the performance of air carrier transitioning pilots who had landing training in a landing maneuver approved simulator was compared with the performance of pilots who had landing training in the aircraft. Forty-eight trainees transitioning to the B-727 aircraft and eighty-seven trainees transitioning to the DC-10 were included in the study. The study results in terms of both objectively measured performance indicants and observer and check-pilot ratings did not demonstrate a clear distinction between the two training groups. The results suggest that, for these highly skilled transitioning pilots, a separate training module in the aircraft may be of dubious value.

Direct Observations of a Dynamically Driven Phase Transition with in situ X-Ray Diffraction in a Simple Ionic Crystal

DOE PAGES

Kalita, Patricia E.; Specht, Paul Elliot; Root, Seth; ...

2017-12-21

Here, we report real-time observations of a phase transition in the ionic solid CaF 2, a model AB 2 structure in high-pressure physics. Synchrotron x-ray diffraction coupled with dynamic loading to 27.7 GPa, and separately with static compression, follows, in situ, the fluorite to cotunnite structural phase transition, both on nanosecond and on minute time scales. Using Rietveld refinement techniques, we examine the kinetics and hysteresis of the transition. Our results give insight into the kinetic time scale of the fluorite-cotunnite phase transition under shock compression, which is relevant to a number of isomorphic compounds.

UTM: Universal Transit Modeller

NASA Astrophysics Data System (ADS)

Deeg, Hans J.

2014-12-01

The Universal Transit Modeller (UTM) is a light-curve simulator for all kinds of transiting or eclipsing configurations between arbitrary numbers of several types of objects, which may be stars, planets, planetary moons, and planetary rings. A separate fitting program, UFIT (Universal Fitter) is part of the UTM distribution and may be used to derive best fits to light-curves for any set of continuously variable parameters. UTM/UFIT is written in IDL code and its source is released in the public domain under the GNU General Public License.

Advanced IR System For Supersonic Boundary Layer Transition Flight Experiment

NASA Technical Reports Server (NTRS)

Banks, Daniel W.

2008-01-01

Infrared thermography is a preferred method investigating transition in flight: a) Global and non-intrusive; b) Can also be used to visualize and characterize other fluid mechanic phenomena such as shock impingement, separation etc. F-15 based system was updated with new camera and digital video recorder to support high Reynolds number transition tests. Digital Recording improves image quality and analysis capability and allows for accurate quantitative (temperature) measurements and greater enhancement through image processing allows analysis of smaller scale phenomena.

Detection and Characterization of Boundary-Layer Transition in Flight at Supersonic Conditions Using Infrared Thermography

NASA Technical Reports Server (NTRS)

Banks, Daniel W.

2008-01-01

Infrared thermography is a powerful tool for investigating fluid mechanics on flight vehicles. (Can be used to visualize and characterize transition, shock impingement, separation etc.). Updated onboard F-15 based system was used to visualize supersonic boundary layer transition test article. (Tollmien-Schlichting and cross-flow dominant flow fields). Digital Recording improves image quality and analysis capability. (Allows accurate quantitative (temperature) measurements, Greater enhancement through image processing allows analysis of smaller scale phenomena).

Effects of Parental Separation and Reentry into Union on the Emotional Well-Being of Children.

ERIC Educational Resources Information Center

Baydar, Nazli

1988-01-01

Examined data from two waves of National Survey of Children to investigate impact of family transitions on changes in children's emotional and behavioral problems as reported by mothers. Results revealed gender differences in changes in emotional well-being attributable to transitions. Found that increase in emotional and behavioral problems could…

A Needs-Assessment of Agencies Serving Individuals with Deaf-Blindness: A National Profile of Transitional Services.

ERIC Educational Resources Information Center

Seiler, Lauren H.; And Others

A national needs assessment of 719 educational and adult service agencies providing or proposing to provide transitional services to individuals with deaf-blindness was conducted to determine national and regional technical assistance needs. On average, each agency expressed a need for technical assistance in 20 separate areas. In the area of…

Transition path time distributions

NASA Astrophysics Data System (ADS)

Laleman, M.; Carlon, E.; Orland, H.

2017-12-01

Biomolecular folding, at least in simple systems, can be described as a two state transition in a free energy landscape with two deep wells separated by a high barrier. Transition paths are the short part of the trajectories that cross the barrier. Average transition path times and, recently, their full probability distribution have been measured for several biomolecular systems, e.g., in the folding of nucleic acids or proteins. Motivated by these experiments, we have calculated the full transition path time distribution for a single stochastic particle crossing a parabolic barrier, including inertial terms which were neglected in previous studies. These terms influence the short time scale dynamics of a stochastic system and can be of experimental relevance in view of the short duration of transition paths. We derive the full transition path time distribution as well as the average transition path times and discuss the similarities and differences with the high friction limit.

Experimental Investigation of Transition to Turbulence as Affected by Passing Wakes

NASA Technical Reports Server (NTRS)

Kaszeta, Richard W.; Simon, Terrence W.; Ashpis, David (Technical Monitor)

2002-01-01

Experimental results from a study of the effects of passing wakes upon laminar-to-turbulent transition in a low-pressure turbine passage are presented. The test section geometry is designed to simulate the effects of unsteady wakes resulting from rotor-stator interaction upon laminar-to-turbulent transition in turbine blade boundary layers and separated flow regions over suction surfaces. Single-wire, thermal anemometry techniques were used to measure time-resolved and phase-averaged, wall-normal profiles of velocity, turbulence intensity, and intermittency at multiple streamwise locations over the turbine airfoil suction surface. These data are compared to steady state, wake-free data collected in the same geometry to identify the effects of wakes upon laminar-to-turbulent transition. Results are presented for flows with a Reynolds number based on suction surface length and exit velocity of 50,000 and an approach flow turbulence intensity of 2.5 percent. From these data, the effects of passing wakes and associated increased turbulence levels and varying pressure gradients on transition and separation in the near-wall flow are presented. The results show that the wakes affect transition both by virtue of their difference in turbulence level from that of the free-stream but also by virtue of their velocity deficit relative to the freestream velocity, and the concomitant change in angle of attack and temporal pressure gradients. The results of this study seem to support the theory that bypass transition is a response of the near-wall viscous layer to pressure fluctuations imposed upon it from the free-stream flow. The data also show a significant lag between when the wake is present over the surface and when transition begins. The accompanying CD-ROM includes tabulated data, animations, higher resolution plots, and an electronic copy of this report.

Many shades of green: the dynamic tropical forest–savannah transition zones

PubMed Central

Oliveras, Immaculada; Malhi, Yadvinder

2016-01-01

The forest–savannah transition is the most widespread ecotone in tropical areas, separating two of the most productive terrestrial ecosystems. Here, we review current understanding of the factors that shape this transition, and how it may change under various drivers of local or global change. At broadest scales, the location of the transition is shaped by water availability, mediated strongly at local scales by fire regimes, herbivory pressure and spatial variation in soil properties. The frequently dynamic nature of this transition suggests that forest and savannah can exist as alternative stable states, maintained and separated by fire–grass feedbacks and tree shade–fire suppression feedback. However, this theory is still contested and the relative contributions of the main biotic and abiotic drivers and their interactions are yet not fully understood. These drivers interplay with a wide range of ecological processes and attributes at the global, continental, regional and local scales. The evolutionary history of the biotic and abiotic drivers and processes plays an important role in the current distributions of these transitions as well as in their species composition and ecosystem functioning. This ecotone can be sensitive to shifts in climate and other driving factors, but is also potentially stabilized by negative feedback processes. There is abundant evidence that these transitions are shifting under contemporary global and local changes, but the direction of shift varies according to region. However, it still remains uncertain how these transitions will respond to rapid and multi-faceted ongoing current changes, and how increasing human influence will interact with these shifts. This article is part of the themed issue ‘Tropical grassy biomes: linking ecology, human use and conservation’. PMID:27502373

Dynamical Generation of the Transition Zone in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Hansen, U.; Stemmer, K.

2005-12-01

The internal structure of the Earth is made up by a series of layers, though it is unclear how many layers exist and if there are layers invisible to remote sensing techniques. The transition zone is likely to be a boundary layer separating the convective systems in the lower and upper mantle. It seems likely that currently there is some mass exchange across this boundary, rather than the two systems beeing strictly separated.a Double-diffusive convection(d.d.c) is a vital mechanism which can generate layered structure and may thus be an important mmical machinery behind the formation of the transition zone. Double-diffusive convection determines the dynamics of systems whose density is influenced by at least two components with different molecular diffusivities.In the mantle, composition and temperature play the role of those two components. By means of numerical experiments we demonstrate that under mantle relevant conditions d.d.c typically leads to the formation of a transition zone. The calculations encompass two- and three dimensional Cartesian geometries as well as fully 3D spherical domains. We have further included strongly temperature dependent viscosity and find that this leads to even more pronounced layering. In most cases a layered flow pattern emerges, where two layers with a transition zone in between resembles a quasistationary state. Thus, the transition zone can be the result of a self organization process of the convective flow in the mantle. The presence of a phase transition further helps to stabilize the boundary against overturning, even on a time scale on the order of the age of the Earth.

Correlation-based Transition Modeling for External Aerodynamic Flows

NASA Astrophysics Data System (ADS)

Medida, Shivaji

Conventional turbulence models calibrated for fully turbulent boundary layers often over-predict drag and heat transfer on aerodynamic surfaces with partially laminar boundary layers. A robust correlation-based model is developed for use in Reynolds-Averaged Navier-Stokes simulations to predict laminar-to-turbulent transition onset of boundary layers on external aerodynamic surfaces. The new model is derived from an existing transition model for the two-equation k-omega Shear Stress Transport (SST) turbulence model, and is coupled with the one-equation Spalart-Allmaras (SA) turbulence model. The transition model solves two transport equations for intermittency and transition momentum thickness Reynolds number. Experimental correlations and local mean flow quantities are used in the model to account for effects of freestream turbulence level and pressure gradients on transition onset location. Transition onset is triggered by activating intermittency production using a vorticity Reynolds number criterion. In the new model, production and destruction terms of the intermittency equation are modified to improve consistency in the fully turbulent boundary layer post-transition onset, as well as ensure insensitivity to freestream eddy viscosity value specified in the SA model. In the original model, intermittency was used to control production and destruction of turbulent kinetic energy. Whereas, in the new model, only the production of eddy viscosity in SA model is controlled, and the destruction term is not altered. Unlike the original model, the new model does not use an additional correction to intermittency for separation-induced transition. Accuracy of drag predictions are improved significantly with the use of the transition model for several two-dimensional single- and multi-element airfoil cases over a wide range of Reynolds numbers. The new model is able to predict the formation of stable and long laminar separation bubbles on low-Reynolds number airfoils that is not captured with conventional turbulence models. The validated transition model is successfully applied to rotating blade configurations in axial flow conditions to study the effects of transitional boundary layers on rotor thrust and torque. In helicopter rotors, inclusion of transition effects increased thrust prediction by 2% and decreased torque by as much as 8% at lower collective angles, due to reduced airfoil profile drag. In wind turbine rotors, transition model predicted a 7%--70% increase in generated shaft torque at lower wind speeds, due to lower viscous drag. This has important implications for CFD analysis of small wind turbines operating at low values of rated power. Transition onset locations along upper and lower surfaces of rotor blades are analyzed in detail. A new crossflow transition onset criterion is developed to account for crossflow instability effects in three-dimensional boundary layers. Preliminary results for swept wing and rotating blade flows demonstrate the need to account for crossflow transition in three-dimensional simulations of wings, rotating blades, and airframes. Inclusion of crossflow effects resulted in accelerated transition in the presence of favorable pressure gradients and yawed flow. Finally, a new correction to the wall damping function in the Spalart-Allmaras turbulence model is proposed to improve sensitivity of the model to strong adverse pressure gradients (APG). The correction reduces turbulence production in the boundary layer when the ratio of magnitudes of local turbulent stress to the wall shear stress exceeds a threshold value, therefore enabling earlier separation of boundary layer. Improved prediction of static and dynamic stall on two-dimensional airfoils is demonstrated with the APG correction.

Report on the Conference on the Separating Serviceman Held at the National War College, 29-31 October 1969.

ERIC Educational Resources Information Center

Department of Defense, Washington, DC.

This conference enabled operators of training programs for separating servicemen to "talk shop" among themselves and with outside supporting agencies and organizations, both public and private. Panel discussions and speeches dealt with such matters as local administration of the TRANSITION Program; counseling and placement (including the…

The Annual Third-Year Resident Rampage: A Separation Crisis of Manageable Proportions.

ERIC Educational Resources Information Center

Merkel, William T.; Walbroehl, Gordon S.

1980-01-01

Third-year residents nearing completion of their training and preparing to leave for independent practice often appear to experience anxieties that suggest a form of separation crisis. Their negative behavior may be a way of making the old milieu less welcoming and thus easier to leave. Advice for easing the transition is offered. (JMD)

Strain-induced topological magnon phase transitions: applications to kagome-lattice ferromagnets

NASA Astrophysics Data System (ADS)

Owerre, S. A.

2018-06-01

A common feature of topological insulators is that they are characterized by topologically invariant quantity such as the Chern number and the index. This quantity distinguishes a nontrivial topological system from a trivial one. A topological phase transition may occur when there are two topologically distinct phases, and it is usually defined by a gap closing point where the topologically invariant quantity is ill-defined. In this paper, we show that the magnon bands in the strained (distorted) kagome-lattice ferromagnets realize an example of a topological magnon phase transition in the realistic parameter regime of the system. When spin–orbit coupling (SOC) is neglected (i.e. no Dzyaloshinskii–Moriya interaction), we show that all three magnon branches are dispersive with no flat band, and there exists a critical point where tilted Dirac and semi-Dirac point coexist in the magnon spectra. The critical point separates two gapless magnon phases as opposed to the usual phase transition. Upon the inclusion of SOC, we realize a topological magnon phase transition point at the critical strain , where D and J denote the perturbative SOC and the Heisenberg spin exchange interaction respectively. It separates two distinct topological magnon phases with different Chern numbers for and for . The associated anomalous thermal Hall conductivity develops an abrupt change at , due to the divergence of the Berry curvature in momentum space. The proposed topological magnon phase transition is experimentally feasible by applying external perturbations such as uniaxial strain or pressure.

Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Nykaza, Jacob Richard

In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk electrode (RDE) experiments determined the interfacial resistance imposed during cell assembly between the AEM, catalyst, and ionomer was a factor in fuel cell performance. Further RDE studies investigated the electrochemical stability of the PIL block copolymer ionomer under applied potentials, where it was determined that potential cycling increased the degradation compared to constant voltage or open circuit voltage studies. The PIL diblock copolymer was then anion exchanged to the bis(trifluoromethane)sulfonamide (TFSI-) anion form and imbibed with a lithium salt and ionic liquid solution for use as a SPE in lithium-ion batteries resulting in a maximum discharge capacity of 112 mAh g-1 at 0.1 C with a Coulombic efficiency greater than 94% over 100 cycles. PIL block copolymers have promising mechanical properties and transport properties (i.e., ion conductivity) in both the hydrated (hydrophilic anions; Br-, OH-) and dry (hydrophobic anions; TFSI-) states resulting in highly conductive, chemically/thermally stable, and mechanically robust solid-state polymer separators for use as AEMs in AFCs and as SPEs in lithium-ion batteries.

Troubling Transitions? Young People's Experiences of Growing up in Poverty in Rural Andhra Pradesh, India

ERIC Educational Resources Information Center

Morrow, Virginia

2013-01-01

Global policy attention has begun to focus on young people in developing countries and much of the discourse is framed around notions of "transition to adulthood" based on the idea that individuals develop in linear ways, separate from family and community. This idea has already been widely critiqued in western contexts. This article…

Transitioning between Work and Family Roles as a Function of Boundary Flexibility and Role Salience

ERIC Educational Resources Information Center

Winkel, Doan E.; Clayton, Russell W.

2010-01-01

This study investigates the manner in which people separate their work and family roles and how they manage the boundaries of these two important roles. Specifically, we focus on how role flexibility and salience influence transitions between roles. Results indicate that the ability and willingness to flex a role boundary and role salience are…

Success and Failure in Secondary Education: Socio-Economic Background Effects on Secondary School Outcome in the Netherlands, 1927-1998

ERIC Educational Resources Information Center

Tieben, Nicole; Wolbers, Maarten

2010-01-01

In the Netherlands, educational attainment is the result of a sequence of separate educational transitions. Because of the tracked nature of the Dutch educational system, students do not make binary stay-or-leave-decisions at each transition. After having entered one track of secondary education, students can change tracks during the entire…

WHAT HAPPENS TO CHILDREN IN THE TRANSITION FROM A PREDOMINANTLY RURAL ECONOMY TO MODERN INDUSTRIALIZATION.

ERIC Educational Resources Information Center

SKARD, ASE GRUDE

WESTERN COUNTRIES HAVE NEGLECTED THE CULTURAL DEVELOPMENT OF THEIR CHILDREN IN THE PROCESS OF TRANSITION FROM RURAL TO URBAN LIVING. IN CONTRAST TO THE RURAL CHILD, THE URBAN CHILD EXPERIENCES RESTRICTED MOVEMENT, REDUCED CONTACT WITH ADULTS, SEPARATION FROM ONE OR BOTH PARENTS DURING THE WORK DAY, CONSUMPTION OF GOODS WHILE SELDOM OBSERVING THEIR…

Distributed Low Temperature Combustion: Fundamental Understanding of Combustion Regime Transitions

DTIC Science & Technology

2016-09-07

AFRL-AFOSR-UK-TR-2016-0021 Distributed Low Temperature Combustion 133024 Peter Lindstedt IMPERIAL COLLEGE OF SCIENCE TECHNOLOGY & MEDICINE Final...TYPE Final 3. DATES COVERED (From - To) 01 Feb 2013 to 31 Jul 2016 4. TITLE AND SUBTITLE Distributed Low Temperature Combustion: Fundamental...identification of five separate fluid states. 15. SUBJECT TERMS EOARD, Low Temperature Combustion, Combustion Regime Transitions 16. SECURITY

How kinetics drives the two- to three-dimensional transition in semiconductor strained heterostructures: The case of InAs/GaAs(001)

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

Arciprete, F.; Placidi, E.; Sessi, V.

2006-07-24

The two- to three-dimensional growth mode transition in the InAs/GaAs(001) heterostructure has been investigated by means of atomic force microscopy. The kinetics of the density of three-dimensional islands indicates two transition onsets at 1.45 and 1.59 ML of InAs coverage, corresponding to two separate families, small and large dots. According to the scaling analysis and volume measurements, the transition between the two families of quantum dots and the explosive nucleation of the large ones is triggered by the erosion of the step edges.

Voluntary transition of the CEO: owner CEOs' sense of self before, during and after transition

PubMed Central

Byrnes, Randy T.; Taylor, Scott N.

2015-01-01

This inductive study explores how former business owner chief executive officers (CEOs) experience sense of self during voluntary separation and transition from their company. Our inquiry engaged 16 CEOs who ran companies ranging in size from 15 to 500 employees as they detailed their stories of walking away from roles as owner CEOs. We developed a coding scheme to analyze themes manifested in the narratives. We also analyzed the former CEOs' narratives using a stage and valence model depicting both the continuum of the separation experience and the characterization of each stage as a positive or negative state of being. The diverse yet synchronous stories resulted in three implications for current owner CEOs, professionals who advise CEOs, and future research on CEOs' careers. First, the CEOs often failed to allocate sufficient time and effort to prepare for an identity shift following the sale of their company or transition into retirement. Second, the CEOs experienced a diminished sense of self and dissatisfaction with the exit event. Third, the majority of the CEOs demonstrated an ability to work through the adverse and unanticipated states of being into a positive sense of self. PMID:26579018

[The quality of sibling relation who have experienced family transitions and those who have not].

PubMed

Simard, Marie; Beaudry, Madeleine; Drapeau, Sylvie; Nadeau, France; Charbonneau, Cécile

2002-01-01

In this study, similarities and differences in sibling relationships between children who have experienced family transitions and those who have not are examined. Comparisons are made between children who live in intact families, those whose parents have separated, and those who live in substitute care regarding the quality of their relationships with one of their siblings. More specifically, 4 dimensions describing the quality of sibling relationships are compared: Warmth/Closeness, Conflict, Relative Status/Power, and Rivalry (Furman & Buhrmester, 1985). The sample is made up of 3 groups of children (N = 158) aged between 8 and 12 years old: children living in intact families (n = 101), children who have experienced parental separation (n = 35), and children living in substitute care (n = 22). Results indicate differences on dimensions of Warmth/Closeness, Conflict, and Relative Status/Power. Different patterns of responses between the children who have experienced family transitions and those who have not are observed for the dimensions of Conflict and Power. The significant difference observed between the groups for the dimension of Warmth appears difficult to explain. Discussion of these results emphasizes the importance of the relationship between brothers and sisters experiencing family transition.

Energy barriers between metastable states in first-order quantum phase transitions

NASA Astrophysics Data System (ADS)

Wald, Sascha; Timpanaro, André M.; Cormick, Cecilia; Landi, Gabriel T.

2018-02-01

A system of neutral atoms trapped in an optical lattice and dispersively coupled to the field of an optical cavity can realize a variation of the Bose-Hubbard model with infinite-range interactions. This model exhibits a first-order quantum phase transition between a Mott insulator and a charge density wave, with spontaneous symmetry breaking between even and odd sites, as was recently observed experimentally [Landig et al., Nature (London) 532, 476 (2016), 10.1038/nature17409]. In the present paper, we approach the analysis of this transition using a variational model which allows us to establish the notion of an energy barrier separating the two phases. Using a discrete WKB method, we then show that the local tunneling of atoms between adjacent sites lowers this energy barrier and hence facilitates the transition. Within our simplified description, we are thus able to augment the phase diagram of the model with information concerning the height of the barrier separating the metastable minima from the global minimum in each phase, which is an essential aspect for the understanding of the reconfiguration dynamics induced by a quench across a quantum critical point.

Voluntary transition of the CEO: owner CEOs' sense of self before, during and after transition.

PubMed

Byrnes, Randy T; Taylor, Scott N

2015-01-01

This inductive study explores how former business owner chief executive officers (CEOs) experience sense of self during voluntary separation and transition from their company. Our inquiry engaged 16 CEOs who ran companies ranging in size from 15 to 500 employees as they detailed their stories of walking away from roles as owner CEOs. We developed a coding scheme to analyze themes manifested in the narratives. We also analyzed the former CEOs' narratives using a stage and valence model depicting both the continuum of the separation experience and the characterization of each stage as a positive or negative state of being. The diverse yet synchronous stories resulted in three implications for current owner CEOs, professionals who advise CEOs, and future research on CEOs' careers. First, the CEOs often failed to allocate sufficient time and effort to prepare for an identity shift following the sale of their company or transition into retirement. Second, the CEOs experienced a diminished sense of self and dissatisfaction with the exit event. Third, the majority of the CEOs demonstrated an ability to work through the adverse and unanticipated states of being into a positive sense of self.

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.

PubMed

Brown, Leslie; Earle, Martyn J; Gîlea, Manuela A; Plechkova, Natalia V; Seddon, Kenneth R

2017-08-10

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

The effect of bioadhesive on the interfacial compatibility and pervaporation performance of composite membranes by MD and GCMC simulation.

PubMed

Wang, Baohe; Nie, Yan; Ma, Jing

2018-03-01

Combing molecular dynamics (MD) and Grand Canonical Monte Carlo (GCMC) simulation, the effect of bioadhesive transition layer on the interfacial compatibility of the pervaporation composite membranes, and the pervaporation performance toward penetrant molecules were investigated. In our previous experimental study, the structural stability and permeability selectivity of the composite membranes were considerably enhanced by the introduction of bioadhesive carbopol (CP). In the present study, the interfacial compatibility and the interfacial energies between the chitosan (CS) separation layer, CP transition layer and the support layer were investigated, respectively. The mobility of polymer chains, free volume in bulk and interface regions were evaluated by the mean-square displacement (MSD) and free volume voids (FFV) analysis. The diffusion and sorption behavior of water/ethanol molecules in bulk and interface regions were characterized. The simulation results of membrane structure have good consistency, indicating that the introduction of CP transition layer improved the interfacial compatibility and interaction between the separation layer and the support layer. Comparing the bulk region of the separation layer, the mobility and free volume of the polymer chain in the interface region decreased and thus reduced the swelling of CS active layer, revealing the increased diffusion selectivity toward the permeated water and ethanol molecules. The strong hydrogen bonds interaction between the COOH of the CP transition layer and water molecules increased the adsorption of water molecules in the interface region. The simulation results were quite consistent with the experimental results. Copyright © 2018 Elsevier Inc. All rights reserved.

Engineering topochemical polymerizations using block copolymer templates.

PubMed

Zhu, Liangliang; Tran, Helen; Beyer, Frederick L; Walck, Scott D; Li, Xin; Agren, Hans; Killops, Kato L; Campos, Luis M

2014-09-24

With the aim to achieve rapid and efficient topochemical polymerizations in the solid state, via solution-based processing of thin films, we report the integration of a diphenyldiacetylene monomer and a poly(styrene-b-acrylic acid) block copolymer template for the generation of supramolecular architectural photopolymerizable materials. This strategy takes advantage of non-covalent interactions to template a topochemical photopolymerization that yields a polydiphenyldiacetylene (PDPDA) derivative. In thin films, it was found that hierarchical self-assembly of the diacetylene monomers by microphase segregation of the block copolymer template enhances the topochemical photopolymerization, which is complete within a 20 s exposure to UV light. Moreover, UV-active cross-linkable groups were incorporated within the block copolymer template to create micropatterns of PDPDA by photolithography, in the same step as the polymerization reaction. The materials design and processing may find potential uses in the microfabrication of sensors and other important areas that benefit from solution-based processing of flexible conjugated materials.

Transition to turbulence under low-pressure turbine conditions.

PubMed

Simon, T W; Kaszeta, R W

2001-05-01

In this paper, the topic of laminar to turbulent flow transition, as applied to the design of gas turbines, is discussed. Transition comes about when a flow becomes sufficiently unstable that the orderly vorticity structure of the laminar layer becomes randomly oriented. Vorticity with a streamwise component leads to rapid growth of eddies of a wide range of sizes and eventually to turbulent flow. Under "natural" transition, infinitesimal disturbances of selected frequencies grow. "Bypass transition" is a term coined to describe a similar process, but one driven by strong external disturbances. Transition proceeds so rapidly that the processes associated with "natural" transition seem to be "bypassed." Because the flow environment in the turbine is disturbed by wakes from upstream airfoils, eddies from combustor flows, jets from film cooling, separation zones on upstream airfoils and steps in the duct walls, transition is of the bypass mode. In this paper, we discuss work that has been done to characterize and model bypass transition, as applied to the turbine environment.

Transfers and transitions between child and adult mental health services.

PubMed

Paul, Moli; Ford, Tamsin; Kramer, Tami; Islam, Zoebia; Harley, Kath; Singh, Swaran P

2013-01-01

Transfer of care from one healthcare provider to another is often understood as a suboptimal version of the process of transition. To separate and evaluate concepts of transfer and transition between child and adolescent mental health services (CAMHS) and adult mental health services (AMHS). In a retrospective case-note survey of young people reaching the upper age boundary at six English CAMHS, optimal transition was evaluated using four criteria: continuity of care, parallel care, a transition planning meeting and information transfer. Of 154 cases, 76 transferred to AMHS. Failure to transfer resulted mainly from non-referral by CAMHS (n = 12) and refusal by service users (n = 12) rather than refusal by AMHS (n = 7). Four cases met all criteria for optimal transition, 13 met none; continuity of care (n = 63) was met most often. Transfer was common but good transition rare. Reasons for failure to transfer differ from barriers to transition. Transfer should be investigated alongside transition in research and service development.

Dewetting and spreading transitions for active matter on random pinning substrates.

PubMed

Sándor, Cs; Libál, A; Reichhardt, C; Olson Reichhardt, C J

2017-05-28

We show that sterically interacting self-propelled disks in the presence of random pinning substrates exhibit transitions among a variety of different states. In particular, from a phase separated cluster state, the disks can spread out and homogeneously cover the substrate in what can be viewed as an example of an active matter wetting transition. We map the location of this transition as a function of activity, disk density, and substrate strength, and we also identify other phases including a cluster state, coexistence between a cluster and a labyrinth wetted phase, and a pinned liquid. Convenient measures of these phases include the cluster size, which dips at the wetting-dewetting transition, and the fraction of sixfold coordinated particles, which drops when dewetting occurs.

Vortex flow hysteresis

NASA Technical Reports Server (NTRS)

Cunningham, A. M., Jr.

1986-01-01

An experimental study was conducted to quantify the hysteresis associated with various vortex flow transition points and to determine the effect of planform geometry. The transition points observed consisted of the appearance (or disappearance) of trailing edge vortex burst and the transition to (or from) flat plate or totally separated flows. Flow visualization with smoke injected into the vortices was used to identify the transitions on a series of semi-span models tested in a low speed tunnel. The planforms tested included simple deltas (55 deg to 80 deg sweep), cranked wings with varying tip panel sweep and dihedral, and a straked wing. High speed movies at 1000 frames per second were made of the vortex flow visualization in order to better understand the dynamics of vortex flow, burst and transition.

Morphological instability of GaAs (7 1 1)A: A transition between (1 0 0) and (5 1 1) terraces

NASA Astrophysics Data System (ADS)

Yazdanpanah, V. R.; Wang, Zh. M.; Salamo, G. J.

2005-06-01

We report on the use of reflection high-energy electron diffraction (RHEED) and scanning tunneling microscopy (STM) study that indicates that the GaAs (7 1 1)A is right at the transition between vicinal GaAs (1 0 0) and vicinal GaAs (5 1 1)A surfaces and that a variation of the As overpressure switches the surface morphology between the two vicinal surfaces. The steps on the vicinal (1 0 0) surface have a width of 1.5 nm creating a staircase surface with excellent possibilities for growth of quantum wells. As-rich conditions can be described by vicinal (5 1 1)A surfaces with a width of 3.5 nm. This surface could find applications as a template for quantum wire growth. The observation suggests that the transition between these two morphologies is understandable based on the increase in surface energy of a vicinal (1 0 0) surface as the step separation approaches the dimer reconstructed separation.

Compact Stars with Sequential QCD Phase Transitions.

PubMed

Alford, Mark; Sedrakian, Armen

2017-10-20

Compact stars may contain quark matter in their interiors at densities exceeding several times the nuclear saturation density. We explore models of such compact stars where there are two first-order phase transitions: the first from nuclear matter to a quark-matter phase, followed at a higher density by another first-order transition to a different quark-matter phase [e.g., from the two-flavor color-superconducting (2SC) to the color-flavor-locked (CFL) phase]. We show that this can give rise to two separate branches of hybrid stars, separated from each other and from the nuclear branch by instability regions, and, therefore, to a new family of compact stars, denser than the ordinary hybrid stars. In a range of parameters, one may obtain twin hybrid stars (hybrid stars with the same masses but different radii) and even triplets where three stars, with inner cores of nuclear matter, 2SC matter, and CFL matter, respectively, all have the same mass but different radii.

Evaluation of transition-sensitive eddy-viscosity turbulence models for separated flow in OpenFOAM

NASA Astrophysics Data System (ADS)

Fadhila, H.; Medina, H.; Beechook, A.; Aleksandrova, S.; Benjamin, S.

2017-07-01

A recently published transition-sensitive turbulence model, k-kL-ω-υ2 [1], is implemented in the open-source CFD package OpenFOAM, and its performance is evaluated in comparison with k-kL-ω [2] and υ2- f [3] models. On T3A and T3B flat plate cases, the k-kL-ω-υ2 model gives accurate transitional predictions. On a flapped NACA 23012 aerofoil, it is found to give only a small improvement over the k-kL-ω model (under 5% reduction in error for lift coefficient) compared with experimental results obtained at the Coventry University wind tunnel, showing limited effects of the extra transport equation which was added to sensitise the model to rotation and curvature effects. Assessment of fluctuating kinetic energy and the new wall-normal turbulent velocity scale shows overprediction near the wall compared to the υ2- f model which indicates a delayed prediction of separation.

Method and apparatus for ultrasonic characterization through the thickness direction of a moving web

DOEpatents

Jackson, Theodore; Hall, Maclin S.

2001-01-01

A method and apparatus for determining the caliper and/or the ultrasonic transit time through the thickness direction of a moving web of material using ultrasonic pulses generated by a rotatable wheel ultrasound apparatus. The apparatus includes a first liquid-filled tire and either a second liquid-filled tire forming a nip or a rotatable cylinder that supports a thin moving web of material such as a moving web of paper and forms a nip with the first liquid-filled tire. The components of ultrasonic transit time through the tires and fluid held within the tires may be resolved and separately employed to determine the separate contributions of the two tire thicknesses and the two fluid paths to the total path length that lies between two ultrasonic transducer surfaces contained within the tires in support of caliper measurements. The present invention provides the benefit of obtaining a transit time and caliper measurement at any point in time as a specimen passes through the nip of rotating tires and eliminates inaccuracies arising from nonuniform tire circumferential thickness by accurately retaining point-to-point specimen transit time and caliper variation information, rather than an average obtained through one or more tire rotations. Morever, ultrasonic transit time through the thickness direction of a moving web may be determined independent of small variations in the wheel axle spacing, tire thickness, and liquid and tire temperatures.

The use of dihexyldithiocarbamate in reverse-phase HPLC of metal chelates

NASA Astrophysics Data System (ADS)

Fatimah, S. S.; Bahti, H. H.; Hastiawan, I.; Permanasari, A.

2018-05-01

Dialkyldithiocarbamates have long been used as chelating agents in reverse-phase HPLC of transition metals. In the previous study, an alkyl homolog of this type of ligand, namely dihexyldithiocarbamate (DHDTC), was synthesized and characterized. The use of this particular ligand in the revese-phase HPLC of some selected transition metal ions is now reported for the first time. The mobile phase comprising of the flow rate and of the detection, in the separation of the metal chelates of Cd (II), Fe (III), Cu (II), and Co (III), were investigated on a C-18 column. The results showed that dihexylditiocarbamate could be used for separating Cd (II), Fe(III), Cu(II), and Co(III). Therefore, it could be used in simultaneous analysis.

Path-length-resolved dynamic light scattering in highly scattering random media: The transition to diffusing wave spectroscopy

NASA Astrophysics Data System (ADS)

Bizheva, Kostadinka K.; Siegel, Andy M.; Boas, David A.

1998-12-01

We used low coherence interferometry to measure Brownian motion within highly scattering random media. A coherence gate was applied to resolve the optical path-length distribution and to separate ballistic from diffusive light. Our experimental analysis provides details on the transition from single scattering to light diffusion and its dependence on the system parameters. We found that the transition to the light diffusion regime occurs at shorter path lengths for media with higher scattering anisotropy or for larger numerical aperture of the focusing optics.

[Family formation and dissolution: the two transitions].

PubMed

Lesthaeghe, R

1987-01-01

"The position is defended which considers the changes in fertility, family formation and dissolution since the previous century as expressions of two separate transitions. The first corresponds with a period of increased qualitative aspirations within the nuclear family, whereas the second transition, carried by the postwar generations, is the expression of growing secular individualism and the preoccupation with self-fulfilment. This corresponds largely with the view held by the French historian Ph. Aries." The geographical focus is on developed countries, primarily non-Communist Europe. (SUMMARY IN ENG AND FRE) excerpt

Engineering topological defect patterns of Bose condensates in shaken optical lattices

NASA Astrophysics Data System (ADS)

Feng, Lei; Clark, Logan W.; Gaj, Anita; Chin, Cheng

2017-04-01

Topological defects emerge and play an essential role in the dynamics of systems undergoing continuous, symmetry-breaking phase transitions. Here, we study the topological defects (domain walls) which form when a Bose condensate in a shaken optical lattice undergoes a quantum phase transition and separates into domains of superfluid with finite momentum. Here, we experimentally demonstrate the ability to control the pattern of domain walls using a digital micromirror device. We further explore implementations of this technique to study dynamics near the phase transition and the evolution of topological defects.

Vertical coupling and transition energies in multilayer InAs/GaAs quantum-dot structures

NASA Astrophysics Data System (ADS)

Taddei, S.; Colocci, M.; Vinattieri, A.; Bogani, F.; Franchi, S.; Frigeri, P.; Lazzarini, L.; Salviati, G.

2000-10-01

Vertically ordered quantum dots in multilayer InAs/GaAs structures have attracted large interest in recent years for device application as light emitters. Contradictory claims on the dependence of the fundamental transition energy on the interlayer separation and number of dot layers have been reported in the literature. We show that either a blueshift or a redshift of the fundamental transition energy can be observed in different coupling conditions and straightforwardly explained by including strain, indium segregation, and electron-hole Coulomb interaction, in good agreement with experimental results.

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

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

Changes in Smoking Behavior over Family Transitions: Evidence for Anticipation and Adaptation Effects.

PubMed

Bricard, Damien; Legleye, Stéphane; Khlat, Myriam

2017-06-07

The study of changes in smoking behaviors over the life course is a promising line of research. This paper aims to analyze the temporal relation between family transitions (partnership formation, first childbirth, separation) and changes in smoking initiation and cessation. We propose a discrete-time logistic model to explore the timing of changes in terms of leads and lags effects up to three years around the event in order to measure both anticipation and adaptation mechanisms. Retrospective biographical data from the Santé et Itinéraires Professionnels (SIP) survey conducted in France in 2006 are used. Partnership formation was followed for both genders by a fall in smoking initiation and an immediate rise in smoking cessation. Childbirth was associated with increased smoking cessation immediately around childbirth, and additionally, females showed an anticipatory increase in smoking cessation up to two years before childbirth. Couple separation was accompanied by an anticipatory increase in smoking initiation for females up to two years prior to the separation, but this effect only occurred in males during separation. Our findings highlight opportunities for more targeted interventions over the life course to reduce smoking, and therefore have relevance for general practitioners and public policy elaboration.

Military to civilian nurse: Personal and professional reconstruction.

PubMed

Elliott, Brenda; Chargualaf, Katie A; Patterson, Barbara

2017-05-01

To examine and describe the transition process of military nurses from military nursing practice to civilian nursing practice. A second aim was to identify challenges and facilitators to this transition. Serving in the military, and embodying its values, can have a major impact on a person's worldview. These individuals serve not only as nurses but also as part of a larger military culture with a mission to protect. The decision to separate from the military and transition into the civilian workforce carries many challenges capable of influencing nurses' personal and professional identities. Qualitative descriptive. Semi-structured interviews of 10 nurse veterans were conducted in 2015-2016. Data were collected until saturation was reached. The transition includes four major phases from military to civilian nurse: Separating from Military Life, Conflict and Chaos, Shifting Sands and Personal and Professional Reconstruction. Duration and progress through each phase varied slightly for individual nurses. Both work-role and personal identity transition occur when a nurse leaves the military and enters civilian practice. Military and civilian organisations, in both the USA and other countries, can implement supports to aid these nurses during this personal and professional change. Recommendations from the study group are provided. The global nursing profession, as well as healthcare organisations that employ nurse veterans, has a commitment and obligation to understand the transition process of nurses who practise within the scope of military nursing and later in civilian nursing environments so that they may be supported and used to the extent of their prior experience. Lessons learned and advice from this group of nurses may positively aid others in their transition experience. © 2016 John Wiley & Sons Ltd.

EXTRASOLAR BINARY PLANETS. II. DETECTABILITY BY TRANSIT OBSERVATIONS

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

Lewis, K. M.; Ida, S.; Ochiai, H.

2015-05-20

We discuss the detectability of gravitationally bound pairs of gas-giant planets (which we call “binary planets”) in extrasolar planetary systems that are formed through orbital instability followed by planet–planet dynamical tides during their close encounters, based on the results of N-body simulations by Ochiai et al. (Paper I). Paper I showed that the formation probability of a binary is as much as ∼10% for three giant planet systems that undergo orbital instability, and after post-capture long-term tidal evolution, the typical binary separation is three to five times the sum of the physical radii of the planets. The binary planets aremore » stable during the main-sequence lifetime of solar-type stars, if the stellarcentric semimajor axis of the binary is larger than 0.3 AU. We show that detecting modulations of transit light curves is the most promising observational method to detect binary planets. Since the likely binary separations are comparable to the stellar diameter, the shape of the transit light curve is different from transit to transit, depending on the phase of the binary’s orbit. The transit durations and depth for binary planet transits are generally longer and deeper than those for the single planet case. We point out that binary planets could exist among the known inflated gas-giant planets or objects classified as false positive detections at orbital radii ≳0.3 AU, propose a binary planet explanation for the CoRoT candidate SRc01 E2 1066, and show that binary planets are likely to be present in, and could be detected using, Kepler-quality data.« less

Electronic Structure at Oxide Interfaces

DTIC Science & Technology

2014-06-01

of materials with desired correlated electron properties such as ferromagnetism with a high Curie temperature, high transition temperature...approximation and therefore the canonical Mott picture is unable to account for the insulating behavior of these materials . We resolve this apparent...the two materials . LaTiO3 shows insulating behavior with a small excitation gap set by Ti d-d transitions and a wide energy separation between Ti d

Accurate Theoretical Predictions of the Properties of Energetic Materials

DTIC Science & Technology

2008-09-18

decomposition, Monte Carlo, molecular dynamics, supercritical fluids, solvation and separation, quantum Monte Carlo, potential energy surfaces, RDX , TNAZ...labs, who are contributing to the theoretical efforts, providing data for testing of the models, or aiding in the transition of the methods, models...and results to DoD applications. The major goals of the project are: • Models that describe phase transitions and chemical reactions in

Using the 2016 Transit of Mercury to Find the Distance to the Sun

ERIC Educational Resources Information Center

Pasachoff, Jay M.; Gährken, Bernd; Schneider, Glenn

2017-01-01

In this article, the authors describe their use of simultaneous observations of the 2016 transit of Mercury made from two widely separated locations on Earth to determine the distance to the Sun in a way different from that suggested in 1715 by Halley. Using an internet link, teachers and students can make a similar derivation at the 2019 transit…

Separation and Identification of a Mixture of Group 6 Transition-Metal Carbonyl Compounds Using GC-MS in the General Chemistry Curriculum

ERIC Educational Resources Information Center

Fong, Lawrence K.

2004-01-01

Students in the general chemistry course are advised to scrutinize data obtained by gas chromatograph (GC) for segregation, and mass spectroscopy (MS) for recognizing combination of group 6 transition-metal carbonyl compounds. The GC-MS method arouses students' interest, as it can be applied to real-world situations, such as the routine…

An investigation of nonsimultaneous laser-induced fluorescence

NASA Technical Reports Server (NTRS)

Fletcher, D. G.

1993-01-01

An alternative to simultaneous, two-line laser-induced fluorescence for thermodynamic property measurement is presented. This spectroscopic approach is similar to multiple-overheat hot-wire anemometry and is based on laser excitation of different fluorescence transitions for separate, sequential wind tunnel runs. Both fluctuating and mean thermodynamic property measurements seem to be achievable with this method without exciting the transitions during the same laser pulse.

Movie of phase separation during physics of colloids in space experiment

NASA Technical Reports Server (NTRS)

2002-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area in the video is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Phase separation during the Experiment on Physics of Colloids in Space

NASA Technical Reports Server (NTRS)

2003-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Reynolds-averaged Navier-Stokes investigation of high-lift low-pressure turbine blade aerodynamics at low Reynolds number

NASA Astrophysics Data System (ADS)

Arko, Bryan M.

Design trends for the low-pressure turbine (LPT) section of modern gas turbine engines include increasing the loading per airfoil, which promises a decreased airfoil count resulting in reduced manufacturing and operating costs. Accurate Reynolds-Averaged Navier-Stokes predictions of separated boundary layers and transition to turbulence are needed, as the lack of an economical and reliable computational model has contributed to this high-lift concept not reaching its full potential. Presented here for what is believed to be the first time applied to low-Re computations of high-lift linear cascade simulations is the Abe-Kondoh-Nagano (AKN) linear low-Re two-equation turbulence model which utilizes the Kolmogorov velocity scale for improved predictions of separated boundary layers. A second turbulence model investigated is the Kato-Launder modified version of the AKN, denoted MPAKN, which damps turbulent production in highly strained regions of flow. Fully Laminar solutions have also been calculated in an effort to elucidate the transitional quality of the turbulence model solutions. Time accurate simulations of three modern high-lift blades at a Reynolds number of 25,000 are compared to experimental data and higher-order computations in order to judge the accuracy of the results, where it is shown that the RANS simulations with highly refined grids can produce both quantitatively and qualitatively similar separation behavior as found in experiments. In particular, the MPAKN model is shown to predict the correct boundary layer behavior for all three blades, and evidence of transition is found through inspection of the components of the Reynolds Stress Tensor, spectral analysis, and the turbulence production parameter. Unfortunately, definitively stating that transition is occurring becomes an uncertain task, as similar evidence of the transition process is found in the Laminar predictions. This reveals that boundary layer reattachment may be a result of laminar vortex shedding interaction with the blade surface, or that application of Laminar solvers with highly refined grids may be valid for investigations of transitional flow. It is recommended that this be studied in the future along with further studies of the turbulence models presented, which have proved to be worthy of additional study in the present application.

KELT-21b: A Hot Jupiter Transiting the Rapidly Rotating Metal-poor Late-A Primary of a Likely Hierarchical Triple System

NASA Astrophysics Data System (ADS)

Johnson, Marshall C.; Rodriguez, Joseph E.; Zhou, George; Gonzales, Erica J.; Cargile, Phillip A.; Crepp, Justin R.; Penev, Kaloyan; Stassun, Keivan G.; Gaudi, B. Scott; Colón, Knicole D.; Stevens, Daniel J.; Strassmeier, Klaus G.; Ilyin, Ilya; Collins, Karen A.; Kielkopf, John F.; Oberst, Thomas E.; Maritch, Luke; Reed, Phillip A.; Gregorio, Joao; Bozza, Valerio; Calchi Novati, Sebastiano; D’Ago, Giuseppe; Scarpetta, Gaetano; Zambelli, Roberto; Latham, David W.; Bieryla, Allyson; Cochran, William D.; Endl, Michael; Tayar, Jamie; Serenelli, Aldo; Silva Aguirre, Victor; Clarke, Seth P.; Martinez, Maria; Spencer, Michelle; Trump, Jason; Joner, Michael D.; Bugg, Adam G.; Hintz, Eric G.; Stephens, Denise C.; Arredondo, Anicia; Benzaid, Anissa; Yazdi, Sormeh; McLeod, Kim K.; Jensen, Eric L. N.; Hancock, Daniel A.; Sorber, Rebecca L.; Kasper, David H.; Jang-Condell, Hannah; Beatty, Thomas G.; Carroll, Thorsten; Eastman, Jason; James, David; Kuhn, Rudolf B.; Labadie-Bartz, Jonathan; Lund, Michael B.; Mallonn, Matthias; Pepper, Joshua; Siverd, Robert J.; Yao, Xinyu; Cohen, David H.; Curtis, Ivan A.; DePoy, D. L.; Fulton, Benjamin J.; Penny, Matthew T.; Relles, Howard; Stockdale, Christopher; Tan, Thiam-Guan; Villanueva, Steven, Jr.

2018-02-01

We present the discovery of KELT-21b, a hot Jupiter transiting the V = 10.5 A8V star HD 332124. The planet has an orbital period of P = 3.6127647 ± 0.0000033 days and a radius of {1.586}-0.040+0.039 {R}{{J}}. We set an upper limit on the planetary mass of {M}P< 3.91 {M}{{J}} at 3σ confidence. We confirmed the planetary nature of the transiting companion using this mass limit and Doppler tomographic observations to verify that the companion transits HD 332124. These data also demonstrate that the planetary orbit is well-aligned with the stellar spin, with a sky-projected spin–orbit misalignment of λ =-{5.6}-1.9+1.7\\circ . The star has {T}{eff}={7598}-84+81 K, {M}* ={1.458}-0.028+0.029 {M}ȯ , {R}* =1.638 +/- 0.034 {R}ȯ , and v\\sin {I}* =146 km s‑1, the highest projected rotation velocity of any star known to host a transiting hot Jupiter. The star also appears to be somewhat metal poor and α-enhanced, with [{Fe}/{{H}}]=-{0.405}-0.033+0.032 and [α/Fe] = 0.145 ± 0.053 these abundances are unusual, but not extraordinary, for a young star with thin-disk kinematics like KELT-21. High-resolution imaging observations revealed the presence of a pair of stellar companions to KELT-21, located at a separation of 1.″2 and with a combined contrast of {{Δ }}{K}S=6.39+/- 0.06 with respect to the primary. Although these companions are most likely physically associated with KELT-21, we cannot confirm this with our current data. If associated, the candidate companions KELT-21 B and C would each have masses of ∼0.12 {M}ȯ , a projected mutual separation of ∼20 au, and a projected separation of ∼500 au from KELT-21. KELT-21b may be one of only a handful of known transiting planets in hierarchical triple stellar systems.

Phase-separation induced extraordinary toughening of magnetic hydrogels

NASA Astrophysics Data System (ADS)

Tang, Jingda; Li, Chenghai; Li, Haomin; Lv, Zengyao; Sheng, Hao; Lu, Tongqing; Wang, T. J.

2018-05-01

Phase separation markedly influences the physical properties of hydrogels. Here, we find that poly (N, N-dimethylacrylamide) (PDMA) hydrogels suffer from phase separation in aqueous sodium hydroxide solutions when the concentration is higher than 2 M. The polymer volume fraction and mechanical properties show an abrupt change around the transition point. We utilize this phase separation mechanism to synthesize tough magnetic PDMA hydrogels with the in-situ precipitation method. For comparison, we also prepared magnetic poly (2-acrylamido-2-methyl-propane sulfonic acid sodium) (PNaAMPS) magnetic hydrogels, where no phase separation occurs. The phase-separated magnetic PDMA hydrogels exhibit an extraordinarily high toughness of ˜1000 J m-2; while non-phase-separated magnetic PNaAMPS hydrogels only show a toughness of ˜1 J m-2, three orders of magnitude lower than that of PDMA hydrogels. This phase separation mechanism may become a new approach to prepare tough magnetic hydrogels and inspire more applications.

Theoretical L-shell Coster-Kronig energies 11 or equal to z or equal to 103

NASA Technical Reports Server (NTRS)

Chen, M. H.; Crasemann, B.; Huang, K. N.; Aoyagi, M.; Mark, H.

1976-01-01

Relativistic relaxed-orbital calculations of L-shell Coster-Kronig transition energies have been performed for all possible transitions in atoms with atomic numbers. Hartree-Fock-Slater wave functions served as zeroth-order eigenfunctions to compute the expectation of the total Hamiltonian. A first-order approximation to the local approximation was thus included. Quantum-electrodynamic corrections were made. Each transition energy was computed as the difference between results of separate self-consistent-field calculations for the initial, singly ionized state and the final two-hole state. The following quantities are listed: total transition energy, 'electric' (Dirac-Hartree-Fock-Slater) contribution, magnetic and retardation contributions, and contributions due to vacuum polarization and self energy.

Universality of oscillating boiling in Leidenfrost transition

NASA Astrophysics Data System (ADS)

Tran, Tuan; Khavari, Mohammad

2017-11-01

The Leidenfrost transition leads a boiling system to the boiling crisis, a state in which the liquid loses contact with the heated surface due to excessive vapor generation. Here, using experiments of liquid droplets boiling on a heated surface, we report a new phenomenon, termed oscillating boiling, at the Leidenfrost transition. We show that oscillating boiling results from the competition between two effects: separation of liquid from the heated surface due to localized boiling, and rewetting. We argue theoretically that the Leidenfrost transition can be predicted based on its link with the oscillating boiling phenomenon, and verify the prediction experimentally for various liquids. This work was funded by Nanyang Technological University and A*STAR, Singapore.

Strain-induced topological magnon phase transitions: applications to kagome-lattice ferromagnets.

PubMed

Owerre, S A

2018-06-20

A common feature of topological insulators is that they are characterized by topologically invariant quantity such as the Chern number and the [Formula: see text] index. This quantity distinguishes a nontrivial topological system from a trivial one. A topological phase transition may occur when there are two topologically distinct phases, and it is usually defined by a gap closing point where the topologically invariant quantity is ill-defined. In this paper, we show that the magnon bands in the strained (distorted) kagome-lattice ferromagnets realize an example of a topological magnon phase transition in the realistic parameter regime of the system. When spin-orbit coupling (SOC) is neglected (i.e. no Dzyaloshinskii-Moriya interaction), we show that all three magnon branches are dispersive with no flat band, and there exists a critical point where tilted Dirac and semi-Dirac point coexist in the magnon spectra. The critical point separates two gapless magnon phases as opposed to the usual phase transition. Upon the inclusion of SOC, we realize a topological magnon phase transition point at the critical strain [Formula: see text], where D and J denote the perturbative SOC and the Heisenberg spin exchange interaction respectively. It separates two distinct topological magnon phases with different Chern numbers for [Formula: see text] and for [Formula: see text]. The associated anomalous thermal Hall conductivity develops an abrupt change at [Formula: see text], due to the divergence of the Berry curvature in momentum space. The proposed topological magnon phase transition is experimentally feasible by applying external perturbations such as uniaxial strain or pressure.

Transitions in sex determination and sex chromosomes across vertebrate species.

PubMed

Pennell, Matthew W; Mank, Judith E; Peichel, Catherine L

2018-02-16

Despite the prevalence of sexual reproduction across eukaryotes, there is a remarkable diversity of sex-determination mechanisms. The underlying causes of this diversity remain unclear, and it is unknown whether there are convergent trends in the directionality of turnover in sex-determination mechanisms. We used the recently assembled Tree of Sex database to assess patterns in the evolution of sex-determination systems in the remarkably diverse vertebrate clades of teleost fish, squamate reptiles and amphibians. Contrary to theoretical predictions, we find no evidence that the evolution of separate sexes is irreversible, as transitions from separate sexes to hermaphroditism occur at higher rates than the reverse in fish. We also find that transitions from environmental sex determination to genetic sex determination occur at higher rates than the reverse in both squamates and fish, suggesting that genetic sex determination is more stable. However, our data are not consistent with the hypothesis that heteromorphic sex chromosomes are an "evolutionary trap." Rather, we find similar transition rates between homomorphic and heteromorphic sex chromosomes in both fish and amphibians, and to environmental sex determination from heteromorphic vs. homomorphic sex chromosome systems in fish. Finally, we find that transitions between male and female heterogamety occur at similar rates in amphibians and squamates, while transitions to male heterogamety occur at higher rates in fish. Together, these results provide the most comprehensive view to date of the evolution of vertebrate sex determination in a phylogenetic context, providing new insight into long-standing questions about the evolution of sexual reproduction. © 2018 John Wiley & Sons Ltd.

Wetting Transitions in ^4He/^3He Mixtures on Cesium

NASA Astrophysics Data System (ADS)

Ross, David

1997-03-01

Over the last several years, helium on cesium has proven to be an ideal model system for the study of wetting and wetting transitions(E. Cheng, M.W. Cole, W.F. Saam, and J. Treiner, Phys. Rev. Lett. 67), 1007 (1991).^,(J.E. Rutledge and P. Taborek, Phys. Rev. Lett. 69), 937 (1992).^,(D. Ross, J.E. Rutledge, and P. Taborek, Phys. Rev. Lett. 76), 2350 (1996).. This presentation will focus on the adsorption of binary liquid mixtures of the helium isotopes, ^3He and ^4He, on cesium substrates over a range of temperatures extending from 0.2 K to 1.0 K. The results, spanning ^3He concentrations from 0 to 1, constitute the first experimentally constructed complete wetting phase diagram for a two component liquid at a weakly binding substrate. The wetting behavior is particularly interesting in the vicinity of bulk liquid phase separation. A wetting transition of the ^4He rich liquid between the ^3He rich liquid and the cesium substrate has been found with Tw = 0.53 K. The surface phase transition line associated with this wetting transition is found to extend to both sides of the bulk phase separation line. On the ^3He rich side it is a prewetting line, and on the ^4He rich side it becomes a line of triple point induced dewetting transitions. General arguments indicate that this behavior should be typical of a large class of binary liquid mixtures at weakly binding substrates.

A steadying effect of acoustic excitation on transitory stall

NASA Technical Reports Server (NTRS)

Zaman, K. B. M. Q.

1991-01-01

The effect of acoustic excitation on a class of separated flows with a transitional boundary layer at the point of separation is considered. Experimental results on the flow over airfoils, a two-dimensional backward-facing step, and through large angle conical diffusers are presented. In all cases, the separated flow undergoes large amplitude fluctuations, much of the energy being concentrated at unusually low frequencies. In each case, an appropriate high frequency acoustic excitation is found to be effective in reducing the fluctuations substantially. The effective excitation frequency scales on the initial boundary layer thickness and the effect is apparently achieved through acoustic tripping of the separating boundary layer.

Separation of variables for the Dirac equation in an extended class of Lorentzian metrics with local rotational symmetry

NASA Astrophysics Data System (ADS)

Iyer, B. R.; Kamran, N.

1991-09-01

The question of the separability of the Dirac equation in metrics with local rotational symmetry is reexamined by adapting the analysis of Kamran and McLenaghan [J. Math. Phys. 25, 1019 (1984)] for the metrics admitting a two-dimensional Abelian local isometry group acting orthogonally transitively. This generalized treatment, which involves the choice of a suitable system of local coordinates and spinor frame, allows one to establish the separability of the Dirac equation within the class of metrics for which the previous analysis of Iyer and Vishveshwara [J. Math. Phys. 26, 1034 (1985)] had left the question of separability open.

Fundamental Physics

NASA Image and Video Library

2003-01-22

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Cation–Eutectic Transition via Sublattice Melting in CuInP 2S 6/In 4/3P 2S 6 van der Waals Layered Crystals

DOE PAGES

Susner, Michael A.; Chyasnavichyus, Marius; Puretzky, Alexander A.; ...

2017-07-07

Single crystals of the van der Waals layered ferrielectric material CuInP 2S 6 spontaneously phase separate when synthesized with Cu deficiency. In this paper, we identify a route to form and tune intralayer heterostructures between the corresponding ferrielectric (CuInP 2S 6) and paraelectric (In 4/3P 2S 6) phases through control of chemical phase separation. We conclusively demonstrate that Cu-deficient Cu 1–xIn 1+x/3P 2S 6 forms a single phase at high temperature. We also identify the mechanism by which the phase separation proceeds upon cooling. Above 500 K both Cu + and In 3+ become mobile, while P 2S 6 4–more » anions maintain their structure. We therefore propose that this transition can be understood as eutectic melting on the cation sublattice. Such a model suggests that the transition temperature for the melting process is relatively low because it requires only a partial reorganization of the crystal lattice. As a result, varying the cooling rate through the phase transition controls the lateral extent of chemical domains over several decades in size. At the fastest cooling rate, the dimensional confinement of the ferrielectric CuInP 2S 6 phase to nanoscale dimensions suppresses ferrielectric ordering due to the intrinsic ferroelectric size effect. Finally, intralayer heterostructures can be formed, destroyed, and re-formed by thermal cycling, thus enabling the possibility of finely tuned ferroic structures that can potentially be optimized for specific device architectures.« less

Cation–Eutectic Transition via Sublattice Melting in CuInP 2S 6/In 4/3P 2S 6 van der Waals Layered Crystals

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

Susner, Michael A.; Chyasnavichyus, Marius; Puretzky, Alexander A.

Single crystals of the van der Waals layered ferrielectric material CuInP 2S 6 spontaneously phase separate when synthesized with Cu deficiency. In this paper, we identify a route to form and tune intralayer heterostructures between the corresponding ferrielectric (CuInP 2S 6) and paraelectric (In 4/3P 2S 6) phases through control of chemical phase separation. We conclusively demonstrate that Cu-deficient Cu 1–xIn 1+x/3P 2S 6 forms a single phase at high temperature. We also identify the mechanism by which the phase separation proceeds upon cooling. Above 500 K both Cu + and In 3+ become mobile, while P 2S 6 4–more » anions maintain their structure. We therefore propose that this transition can be understood as eutectic melting on the cation sublattice. Such a model suggests that the transition temperature for the melting process is relatively low because it requires only a partial reorganization of the crystal lattice. As a result, varying the cooling rate through the phase transition controls the lateral extent of chemical domains over several decades in size. At the fastest cooling rate, the dimensional confinement of the ferrielectric CuInP 2S 6 phase to nanoscale dimensions suppresses ferrielectric ordering due to the intrinsic ferroelectric size effect. Finally, intralayer heterostructures can be formed, destroyed, and re-formed by thermal cycling, thus enabling the possibility of finely tuned ferroic structures that can potentially be optimized for specific device architectures.« less

Modeling of near wall turbulence and modeling of bypass transition

NASA Technical Reports Server (NTRS)

Yang, Z.

1992-01-01

The objectives for this project are as follows: (1) Modeling of the near wall turbulence: We aim to develop a second order closure for the near wall turbulence. As a first step of this project, we try to develop a kappa-epsilon model for near wall turbulence. We require the resulting model to be able to handle both near wall turbulence and turbulent flows away from the wall, computationally robust, and applicable for complex flow situations, flow with separation, for example, and (2) Modeling of the bypass transition: We aim to develop a bypass transition model which contains the effect of intermittency. Thus, the model can be used for both the transitional boundary layers and the turbulent boundary layers. We require the resulting model to give a good prediction of momentum and heat transfer within the transitional boundary and a good prediction of the effect of freestream turbulence on transitional boundary layers.

VizieR Online Data Catalog: ExoMol. XVII: SO3 (Underwood+, 2016)

NASA Astrophysics Data System (ADS)

Underwood, D. S.; Yurchenko, S. N.; Tennyson, J.; Al-Refaie, A. F.; Clausen, S.; Fateev, A.

2017-01-01

Because of their size, the transitions are listed in 500 separate files, each containing all the transitions in a 10cm-1 frequency range. These and their contents are ordered by increasing frequency. The name of the file includes the highest frequency in the range; thus the a-4690.dat file contains all the transitions of SO3 in the frequency range 4680-4690cm-1 but not including 4680cm-1. The transition files a-xxxx.dat contain three columns: the reference number in the energy file of the upper state, that of the lower state and the Einstein A coefficient of the transition. The energy file and the transitions files are bzipped, and need to be extracted before use. We also provide the partition functions for each molecule in the range 0 to 1000K. (3 data files).

Transient Three-Dimensional Startup Side Load Analysis of a Regeneratively Cooled Nozzle

NASA Technical Reports Server (NTRS)

Wang, Ten-See

2008-01-01

The objective of this effort is to develop a computational methodology to capture the startup side load physics and to anchor the computed aerodynamic side loads with the available data from a regeneratively cooled, high-aspect-ratio nozzle, hot-fired at sea level. The computational methodology is based on an unstructured-grid, pressure-based, reacting flow computational fluid dynamics and heat transfer formulation, a transient 5 s inlet history based on an engine system simulation, and a wall temperature distribution to reflect the effect of regenerative cooling. To understand the effect of regenerative wall cooling, two transient computations were performed using the boundary conditions of adiabatic and cooled walls, respectively. The results show that three types of shock evolution are responsible for side loads: generation of combustion wave; transitions among free-shock separation, restricted-shock separation, and simultaneous free-shock and restricted shock separations; along with the pulsation of shocks across the lip, although the combustion wave is commonly eliminated with the sparklers during actual test. The test measured two side load events: a secondary and lower side load, followed by a primary and peak side load. Results from both wall boundary conditions captured the free-shock separation to restricted-shock separation transition with computed side loads matching the measured secondary side load. For the primary side load, the cooled wall transient produced restricted-shock pulsation across the nozzle lip with peak side load matching that of the test, while the adiabatic wall transient captured shock transitions and free-shock pulsation across the lip with computed peak side load 50% lower than that of the measurement. The computed dominant pulsation frequency of the cooled wall nozzle agrees with that of a separate test, while that of the adiabatic wall nozzle is more than 50% lower than that of the measurement. The computed teepee-like formation and the tangential motion of the shocks during lip pulsation also qualitatively agree with those of test observations. Moreover, a third transient computation was performed with a proportionately shortened 1 s sequence, and lower side loads were obtained with the higher ramp rate.

A study of the laminar separation bubble on an airfoil at low Reynolds numbers using flow visualization techniques

NASA Technical Reports Server (NTRS)

Schmidt, Gordon S.; Mueller, Thomas J.

1987-01-01

The use of flow visualization to study separation bubbles is evaluated. The wind tunnel, two NACA 66(3)-018 airfoil models, and kerosene vapor, titanium tetrachloride, and surface flow visualizations techniques are described. The application of the three visualization techniques to the two airfoil models reveals that the smoke and vapor techniques provide data on the location of laminar separation and the onset of transition, and the surface method produces information about the location of turbulent boundary layer separation. The data obtained with the three flow visualization techniques are compared to pressure distribution data and good correlation is detected. It is noted that flow visualization is an effective technique for examining separation bubbles.

Stability of spanwise-modulated flows behind backward-facing steps

NASA Astrophysics Data System (ADS)

Boiko, A. V.; Dovgal, A. V.; Sorokin, A. M.

2017-10-01

An overview and synthesis of researches on development of local vortical disturbances in laminar separated flows downstream of backward-facing steps, in which the velocity field depends essentially on two variables are given. Peculiarities of transition to turbulence in such spatially inhomogeneous separated zones are discussed. The experimental data are supplemented by the linear stability characteristics of model velocity profiles of the separated flow computed using both the classical local formulation and the nonlocal approach based on the Floquet theory for partial differential equations with periodic coefficients. The results clarify the response of the local separated flows to their modulation with stationary geometrical and temperature inhomogeneities. The results can be useful for the development of new methods of laminar separation control.

Evaluation of transition year Canadian test sites. [Saskatchewan Province

NASA Technical Reports Server (NTRS)

Payne, R. W. (Principal Investigator)

1980-01-01

The author has identified the following significant results. The spring small grain proportion accuracy in 15 Saskatchewan test sites was found to be comparable to that of the Large Area Crop Inventory Experiment Phase 3 and Transition Year results in the U.S. spring wheat states. Spring small grain labeling accuracy was 94%, and the direct wheat labeling accuracy was 89%, despite the low barley separation accuracy of 30%.

Revisiting the Vulnerability Ethos in Cross-Sectoral Transition Policies and Practices for Young People in the Era of Marketisation of Education

ERIC Educational Resources Information Center

Brunila, Kristiina; Ikävalko, Elina; Kurki, Tuuli; Mertanen, Katariina; Mikkola, Anna

2016-01-01

The ethos of vulnerability has come to play an increasingly central role in shaping cross-sectoral transition policies and practices related to young people outside of education and working life. Yet the wider effects of this ethos in policies and practices are still rarely analysed. In this article, we draw our data from five separate studies.…

OPTICAL ABSORPTION SPECTRUM OF ANTIFERROMAGNETIC MNF2.

DTIC Science & Technology

separated in energy and easily identifiable, (3) has a very simple ground state, and (4) has a well studied magnon structure, an investigation was...undertaken of the excited states in the hope of observing other magnetic dipole transitions and their accompanying magnon sidebands. This study was...similarities between the magnon sidebands in several excited states of the Mn(+2) ion, and to determine the importance of spin assisted transitions in

Transition Assistance Program. Hearing before the Subcommittee on Education, Training and Employment of the Committee on Veterans' Affairs. House of Representatives, One Hundred Second Congress, Second Session.

ERIC Educational Resources Information Center

Congress of the U.S., Washington, DC. House Committee on Veterans' Affairs.

This congressional hearing reviews the continuing implementation of sections 1142, 1143, and 1144 of Title 10, United States Code, and section 1418(a) of Title 38, the Transition Assistance Program to assist servicemembers separating from the Armed Forces as a result of downsizing. Testimony includes statements, prepared statements, and written…

A reconstruction of sexual modes throughout animal evolution.

PubMed

Sasson, Daniel A; Ryan, Joseph F

2017-12-06

Although most extant animals have separate sexes, simultaneous hermaphrodites can be found in lineages throughout the animal kingdom. However, the sexual modes of key ancestral nodes including the last common ancestor (LCA) of all animals remain unclear. Without these data, it is difficult to infer the reproductive-state transitions that occurred early in animal evolution, and thus a broad understanding of the evolution of animal reproduction remains elusive. In this study, we use a composite phylogeny from four previously published studies, two alternative topologies (ctenophores or sponges as sister to the rest of animals), and multiple phylogenetic approaches to conduct the most extensive analysis to date of the evolution of animal sexual modes. Our analyses clarify the sexual mode of many ancestral animal nodes and allow for sound inferences of modal transitions that have occurred in animal history. Our results also indicate that the transition from separate sexes to hermaphroditism has been more common in animal history than the reverse. These results provide the most complete view of the evolution of animal sexual modes to date and provide a framework for future inquiries into the correlation of these transitions with genes, behaviors, and physiology. These results also suggest that mutations promoting hermaphroditism have historically been more likely to invade gonochoristic populations than vice versa.

Quantum phase transition and protected ideal transport in a Kondo chain

DOE PAGES

Tsvelik, A. M.; Yevtushenko, O. M.

2015-11-30

We study the low energy physics of a Kondo chain where electrons from a one-dimensional band interact with magnetic moments via an anisotropic exchange interaction. It is demonstrated that the anisotropy gives rise to two different phases which are separated by a quantum phase transition. In the phase with easy plane anisotropy, Z2 symmetry between sectors with different helicity of the electrons is broken. As a result, localization effects are suppressed and the dc transport acquires (partial) symmetry protection. This effect is similar to the protection of the edge transport in time-reversal invariant topological insulators. The phase with easy axismore » anisotropy corresponds to the Tomonaga-Luttinger liquid with a pronounced spin-charge separation. The slow charge density wave modes have no protection against localizatioin.« less

Study of transitional doubly-odd /sup 186/Ir and /sup 184/Ir

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

Ben Braham, A.; Bourgeois, C.; Kilcher, P.

1987-12-10

The transitional doubly-odd iridium nuclei with A = 184 and 186 have been studied from the ..beta../sup +//EC decay of the corresponding platinum isotopes using the on-line mass separator ISOCELE. Configurations can be reasonably Attributed to the low-lying states of /sup 184/Ir in agreement with results already known. On the other hand an E3 transition observed in /sup 186/Ir suggests that the known long-lived 1.7h 2/sup -/ state is located at 137.5 keV above the 16h 5/sup +/ state, raising questions about structure of this latter state.

Diels–Alder Reactions of Allene with Benzene and Butadiene: Concerted, Stepwise, and Ambimodal Transition States

PubMed Central

2015-01-01

Multiconfigurational complete active space methods (CASSCF and CASPT2) have been used to investigate the (4 + 2) cycloadditions of allene with butadiene and with benzene. Both concerted and stepwise radical pathways were examined to determine the mechanism of the Diels–Alder reactions with an allene dienophile. Reaction with butadiene occurs via a single ambimodal transition state that can lead to either the concerted or stepwise trajectories along the potential energy surface, while reaction with benzene involves two separate transition states and favors the concerted mechanism relative to the stepwise mechanism via a diradical intermediate. PMID:25216056

Structural analysis of polymer thin films using GISAXS in the tender X-ray region: Concept and design of GISAXS experiments using the tender X-ray energy at BL-15A2 at the Photon Factory

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

Takagi, H., E-mail: takagih@post.kek.jp; Igarashi, N.; Mori, T.

If small angle X-ray scattering (SAXS) utilizing the soft X-ray region is available, advanced and unique experiments, which differ from traditional SAXS methods, can be realized. For example, grazing-incidence small angle X-ray scattering (GISAXS) using hard X-ray is a powerful tool for understanding the nanostructure in both vertical and lateral directions of thin films, while GISAXS utilizing the tender X-ray region (SX-GISAXS) enables depth-resolved analysis as well as a standard GISAXS analysis in thin films. Thus, at BL-15A2 at the Photon Factory, a dedicated diffractometer for SX-GISAXS (above 2.1 keV) was constructed. This diffractometer is composed of four vacuum chambers andmore » can be converted into the vacuum state from the sample chamber in front of the detector surface. Diffractions are clearly observed until 12th peak when measuring collagen by SAXS with an X-ray energy of 2.40 keV and a camera length of 825 mm. Additionally, we conducted the model experiment using SX-GISAXS with an X-ray energy of 2.40 keV to confirm that a poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymer thin film has a microphase-separated structure in the thin film, which is composed of lamellae aligned both parallel and perpendicular to the substrate surface. Similarly, in a polystyrene-poly(methyl methacrylate) block copolymer thin film, SX-GISAXS with 3.60 keV and 5.73 keV revealed that hexagonally packed cylinders are aligned parallel to the substrate surface. The incident angle dependence of the first order peak position of the q{sub z} direction obtained from experiments at various incident X-ray energies agrees very well with the theoretical one calculated from the distorted wave Born approximation.« less

Substrate micropatterns produced by polymer demixing regulate focal adhesions, actin anisotropy, and lineage differentiation of stem cells.

PubMed

Vega, Sebastián L; Arvind, Varun; Mishra, Prakhar; Kohn, Joachim; Sanjeeva Murthy, N; Moghe, Prabhas V

2018-06-12

Stem cells are adherent cells whose multipotency and differentiation can be regulated by numerous microenvironmental signals including soluble growth factors and surface topography. This study describes a simple method for creating distinct micropatterns via microphase separation resulting from polymer demixing of poly(desaminotyrosyl-tyrosine carbonate) (PDTEC) and polystyrene (PS). Substrates with co-continuous (ribbons) or discontinuous (islands and pits) PDTEC regions were obtained by varying the ratio of PDTEC and sacrificial PS. Human mesenchymal stem cells (MSCs) cultured on co-continuous PDTEC substrates for 3 days in bipotential adipogenic/osteogenic (AD/OS) induction medium showed no change in cell morphology but exhibited increased anisotropic cytoskeletal organization and larger focal adhesions when compared to MSCs cultured on discontinuous micropatterns. After 14 days in bipotential AD/OS induction medium, MSCs cultured on co-continuous micropatterns exhibited increased expression of osteogenic markers, whereas MSCs on discontinuous PDTEC substrates showed a low expression of adipogenic and osteogenic differentiation markers. Substrates with graded micropatterns were able to reproduce the influence of local underlying topography on MSC differentiation, thus demonstrating their potential for high throughput analysis. This work presents polymer demixing as a simple, non-lithographic technique to produce a wide range of micropatterns on surfaces with complex geometries to influence cellular and tissue regenerative responses. Gaining a better understanding of how engineered microenvironments influence stem cell differentiation is integral to increasing the use of stem cells and materials in a wide range of tissue engineering applications. In this study, we show the range of topography obtained by polymer demixing is sufficient for investigating how surface topography affects stem cell morphology and differentiation. Our findings show that co-continuous topographies favor early (3-day) cytoskeletal anisotropy and focal adhesion maturation as well as long-term (14-day) expression of osteogenic differentiation markers. Taken together, this study presents a simple approach to pattern topographies that induce divergent responses in stem cell morphology and differentiation. Copyright © 2018. Published by Elsevier Ltd.

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

Samant, Saumil; Strzalka, Joseph; Yager, Kevin G.

Dynamic thermal gradient-based processes for directed self-assembly of block copolymer (BCP) thin films such as cold zone annealing (CZA) have demonstrated much potential for rapidly fabricating highly ordered patterns of BCP domains with facile orientation control. As a demonstration, hexagonally packed predominantly vertical cylindrical morphology, technologically relevant for applications such as membranes and lithography, was achieved in 1 μm thick cylinder-forming PS-b-PMMA (cBCP) films by applying sharp thermal gradients (CZA-Sharp) at optimum sample sweep rates. A thorough understanding of the molecular level mechanisms and pathways of the BCP ordering that occur during this CZA-S process is presented, useful to fullymore » exploit the potential of CZA-S for large-scale BCP-based device fabrication. To that end, we developed a customized CZA-S assembly to probe the dynamic structure evolution and ordering of the PS-b-PMMA cBCP film in situ as it undergoes the CZA-S process using the grazing incidence small-angle X-ray scattering (GISAXS) technique. Four distinct regimes of BCP ordering were observed within the gradient that include microphase separation from an “as cast” unordered state (Regime I), evolution of vertical cylinders under a thermally imposed strain gradient (Regime II), reorientation of a fraction of cylinders due to preferential substrate interactions (Regime III), and finally grain-coarsening on the cooling edge (Regime IV). The ordering pathway in the different regimes is further described within the framework of an energy landscape. A novel aspect of this study is the identification of a grain-coarsening regime on the cooling edge of the gradient, previously obscure in zone annealing studies of BCPs. Furthermore, such insights into the development of highly ordered BCP nanostructures under template-free thermal gradient fields can potentially have important ramifications in the field of BCP-directed self-assembly and self-assembling polymer systems more broadly.« less

Property Enhancement Effects of Side-Chain-Type Naphthalene-Based Sulfonated Poly(arylene ether ketone) on Nafion Composite Membranes for Direct Methanol Fuel Cells.

PubMed

Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Zhao, Chengji; Na, Hui

2017-09-20

Nafion/SNPAEK-x composite membranes were prepared by blending raw Nafion and synthesized side-chain-type naphthalene-based sulfonated poly(arylene ether ketone) with a sulfonation degree of 1.35 (SNPAEK-1.35). The incorporation of SNPAEK-1.35 polymer with ion exchange capacity (IEC) of 2.01 mequiv·g -1 into a Nafion matrix has the property enhancement effects, such as increasing IECs, improving proton conductivity, enhancing mechanical properties, reducing methanol crossover, and improving single cell performance of Nafion. Morphology studies show that Nafion/SNPAEK-x composite membranes exhibit a well-defined microphase separation structure depending on the contents of SNPAEK-1.35 polymer. Among them, Nafion/SNPAEK-7.5% with a bicontinuous morphology exhibits the best comprehensive properties. For example, it shows the highest proton conductivities of 0.092 S cm -1 at 25 °C and 0.163 S cm -1 at 80 °C, which are higher than those of recast Nafion with 0.073 S cm -1 at 25 °C and 0.133 S cm -1 at 80 °C, respectively. Nafion/SNPAEK-5.0% and Nafion/SNPAEK-7.5% membranes display an open circuit voltage of 0.77 V and a maximum power density of 47 mW cm -2 at 80 °C, which are much higher than those of recast Nafion of 0.63 V and 24 mW cm -2 under the same conditions. Nafion/SNPAEK-5.0% membrane also has comparable tensile strength (12.7 MPa) to recast Nafion (13.7 MPa), and higher Young's modulus (330 MPa) than that of recast Nafion (240 MPa). By combining their high proton conductivities, comparable mechanical properties, and good single cell performance, Nafion/SNPAEK-x composite membranes have the potential to be polymer electrolyte materials for direct methanol fuel cell applications.

Anomalous dynamics of aqueous solutions of di-propylene glycol methylether confined in MCM-41 by quasielastic neutron scattering

NASA Astrophysics Data System (ADS)

Swenson, Jan; Elamin, Khalid; Chen, Guo; Lohstroh, Wiebke; Sakai, Victoria Garcia

2014-12-01

The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H2O (or D2O) confined in 28 Å pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0-90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement, but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Å. The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.

Unraveling Structure-Property Relationships in Polymer Blends for Intelligent Materials Design

NASA Astrophysics Data System (ADS)

Irwin, Matthew Tyler

Block polymers provide an accessible route to structured, composite materials by combining two or more components with disparate mechanical, chemical, and electrical properties into a single bulk material with nanoscale domains. However, the characteristic lengthscale of these systems is limited, and the choice of components is restricted to those that are able to undergo microstructural ordering at accessible temperatures. This thesis details routes to overcoming these limitations through the addition of a lithium salt, a blend of homopolymers, or both. Chapter 2 describes a study wherein complex sphere phases such as the Frank-Kasper sigma phase can be observed in otherwise disordered asymmetric block polymers through the addition of a lithium salt. Chapter 3 discusses the development and characterization of a ternary polymer blend of an AB diblock copolymer and A and B homopolymers doped with a lithium salt. Detailed characterization showed that doping blends that are otherwise disordered with lithium salt induced microstructural ordering and largely recovers the phase behavior of traditional ternary polymer blends. A systematic study of the ionic conductivity of the blends at a fixed salt concentration demonstrates that, at a given composition, disordered, yet highly structured blends consistently exhibit better conductivity than polycrystalline morphologies with long range order. Chapter 4 extends the methodology of Chapter 3 and details a systematic study of the effects of cross-linker concentration on the performance of polymer electrolyte membranes produced via polymerization-induced microphase separation that exhibit a highly structured, globally disordered microstructure. Finally, Chapter 5 details efforts to develop a water filtration membrane using a polyethylene template derived from a polymeric bicontinuous microemulsion. Throughout all of this work, the goal is to better understand structure-property relationships at the molecular level in order to ultimately inform design criteria for materials where simultaneous control over morphology and mechanical, chemical, or electrical properties is important.

Anomalous dynamics of aqueous solutions of di-propylene glycol methylether confined in MCM-41 by quasielastic neutron scattering

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

Swenson, Jan, E-mail: jan.swenson@chalmers.se; Elamin, Khalid; Chen, Guo

2014-12-07

The molecular dynamics of solutions of di-propylene glycol methylether (2PGME) and H{sub 2}O (or D{sub 2}O) confined in 28 Å pores of MCM-41 have been studied by quasielastic neutron scattering and differential scanning calorimetry over the concentration range 0–90 wt.% water. This system is of particular interest due to its pronounced non-monotonic concentration dependent dynamics of 2PGME in the corresponding bulk system, showing the important role of hydrogen bonding for the dynamics. In this study we have elucidated how this non-monotonic concentration dependence is affected by the confined geometry. The results show that this behaviour is maintained in the confinement,more » but the slowest diffusive dynamics of 2PGME is now observed at a considerably higher water concentration; at 75 wt.% water in MCM-41 compared to 30 wt.% water in the corresponding bulk system. This difference can be explained by an improper mixing of the two confined liquids. The results suggest that water up to a concentration of about 20 wt.% is used to hydrate the hydrophilic hydroxyl surface groups of the silica pores, and that it is only at higher water contents the water becomes partly mixed with 2PGME. Hence, due to this partial micro-phase separation of the two liquids larger, and thereby slower relaxing, structural entities of hydrogen bonded water and 2PGME molecules can only be formed at higher water contents than in the bulk system. However, the Q-dependence is unchanged with confinement, showing that the nature of the molecular motions is preserved. Thus, there is no indication of localization of the dynamics at length scales of less than 20 Å. The dynamics of both water and 2PGME is strongly dominated by translational diffusion at a temperature of 280 K.« less

Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS

DOE PAGES

Samant, Saumil; Strzalka, Joseph; Yager, Kevin G.; ...

2016-10-31

Dynamic thermal gradient-based processes for directed self-assembly of block copolymer (BCP) thin films such as cold zone annealing (CZA) have demonstrated much potential for rapidly fabricating highly ordered patterns of BCP domains with facile orientation control. As a demonstration, hexagonally packed predominantly vertical cylindrical morphology, technologically relevant for applications such as membranes and lithography, was achieved in 1 μm thick cylinder-forming PS-b-PMMA (cBCP) films by applying sharp thermal gradients (CZA-Sharp) at optimum sample sweep rates. A thorough understanding of the molecular level mechanisms and pathways of the BCP ordering that occur during this CZA-S process is presented, useful to fullymore » exploit the potential of CZA-S for large-scale BCP-based device fabrication. To that end, we developed a customized CZA-S assembly to probe the dynamic structure evolution and ordering of the PS-b-PMMA cBCP film in situ as it undergoes the CZA-S process using the grazing incidence small-angle X-ray scattering (GISAXS) technique. Four distinct regimes of BCP ordering were observed within the gradient that include microphase separation from an “as cast” unordered state (Regime I), evolution of vertical cylinders under a thermally imposed strain gradient (Regime II), reorientation of a fraction of cylinders due to preferential substrate interactions (Regime III), and finally grain-coarsening on the cooling edge (Regime IV). The ordering pathway in the different regimes is further described within the framework of an energy landscape. A novel aspect of this study is the identification of a grain-coarsening regime on the cooling edge of the gradient, previously obscure in zone annealing studies of BCPs. Furthermore, such insights into the development of highly ordered BCP nanostructures under template-free thermal gradient fields can potentially have important ramifications in the field of BCP-directed self-assembly and self-assembling polymer systems more broadly.« less

Modelling the transitional boundary layer

NASA Technical Reports Server (NTRS)

Narasimha, R.

1990-01-01

Recent developments in the modelling of the transition zone in the boundary layer are reviewed (the zone being defined as extending from the station where intermittency begins to depart from zero to that where it is nearly unity). The value of using a new non-dimensional spot formation rate parameter, and the importance of allowing for so-called subtransitions within the transition zone, are both stressed. Models do reasonably well in constant pressure 2-dimensional flows, but in the presence of strong pressure gradients further improvements are needed. The linear combination approach works surprisingly well in most cases, but would not be so successful in situations where a purely laminar boundary layer would separate but a transitional one would not. Intermittency-weighted eddy viscosity methods do not predict peak surface parameters well without the introduction of an overshooting transition function whose connection with the spot theory of transition is obscure. Suggestions are made for further work that now appears necessary for developing improved models of the transition zone.

Folding thermodynamics of model four-strand antiparallel beta-sheet proteins.

PubMed Central

Jang, Hyunbum; Hall, Carol K; Zhou, Yaoqi

2002-01-01

The thermodynamic properties for three different types of off-lattice four-strand antiparallel beta-strand protein models interacting via a hybrid Go-type potential have been investigated. Discontinuous molecular dynamic simulations have been performed for different sizes of the bias gap g, an artificial measure of a model protein's preference for its native state. The thermodynamic transition temperatures are obtained by calculating the squared radius of gyration R(g)(2), the root-mean-squared pair separation fluctuation Delta(B), the specific heat C(v), the internal energy of the system E, and the Lindemann disorder parameter Delta(L). Despite these models' simplicity, they exhibit a complex set of protein transitions, consistent with those observed in experimental studies on real proteins. Starting from high temperature, these transitions include a collapse transition, a disordered-to-ordered globule transition, a folding transition, and a liquid-to-solid transition. The high temperature transitions, i.e., the collapse transition and the disordered-to-ordered globule transition, exist for all three beta-strand proteins, although the native-state geometry of the three model proteins is different. However the low temperature transitions, i.e., the folding transition and the liquid-to-solid transition, strongly depend on the native-state geometry of the model proteins and the size of the bias gap. PMID:11806908

Transition from the diamagnetic insulator to ferromagnetic metal in La1-xSrxCoO3

NASA Astrophysics Data System (ADS)

Knížek, Karel; Jirák, Zdeněk; Hejtmánek, Jiří; Novák, Pavel

2010-05-01

We have analyzed, using the theoretical GGA+U calculations, different configurations of spin states (low-spin, LS; intermediate-spin, IS and high-spin, HS Co) and proposed a model that accounts for magnetic and electric transport properties of perovskite cobaltites upon doping by charge carriers. In particular, it appears that the compositional transition from the diamagnetic LS phase of LaCoO3 to the ferromagnetic metallic IS phase in La1-xSrxCoO3 ( x>0.2) involves the same mechanisms as the high-temperature transition in pure LaCoO3. The process occurs gradually via a phase-separated state, where metallic IS domains stabilized through a charge transfer between Co and Co neighbors coexist with the Co poor regions in the LS ground state (or at higher temperatures, in mixed LS/HS state). This phase separation vanishes when doping in La1-xSrxCoO3 reaches x˜0.2, and a uniform IS phase, analogous to that in pure LaCoO3 in the high-temperature limit, is established.

Ionic effects on the temperature-force phase diagram of DNA.

PubMed

Amnuanpol, Sitichoke

2017-12-01

Double-stranded DNA (dsDNA) undergoes a structural transition to single-stranded DNA (ssDNA) in many biologically important processes such as replication and transcription. This strand separation arises in response either to thermal fluctuations or to external forces. The roles of ions are twofold, shortening the range of the interstrand potential and renormalizing the DNA elastic modulus. The dsDNA-to-ssDNA transition is studied on the basis that dsDNA is regarded as a bound state while ssDNA is regarded as an unbound state. The ground state energy of DNA is obtained by mapping the statistical mechanics problem to the imaginary time quantum mechanics problem. In the temperature-force phase diagram the critical force F c (T) increases logarithmically with the Na + concentration in the range from 32 to 110 mM. Discussing this logarithmic dependence of F c (T) within the framework of polyelectrolyte theory, it inevitably suggests a constraint on the difference between the interstrand separation and the length per unit charge during the dsDNA-to-ssDNA transition.

Flow field investigation in a bulb turbine diffuser

NASA Astrophysics Data System (ADS)

Pereira, M.; Duquesne, P.; Aeschlimann, V.; Deschênes, C.

2017-04-01

An important drop in turbine performances has been measured in a bulb turbine model operated at overload. Previous investigations have correlated the performance drop with diffuser losses, and particularly to the flow separation zone at the diffuser wall. The flow has been investigated in the transition part of the diffuser using two LDV measurement sections. The transition part is a diffuser section that transforms from a circular to a rectangular section. The two measurement sections are at the inlet and outlet of the diffuser transition part. The turbine has been operated at three operating points, which are representative of different flow patterns at the diffuser exit at overload. In addition to the average velocity field, the analysis is conducted based on a backflow occurrence function and on the swirl level. Results reveal a counter-rotating zone in the diffuser, which intensifies with the guide vanes opening. The guide vanes opening induces a modification of the flow phenomena: from a central backflow recirculation zone at the lowest flowrate to a backflow zone induced by flow separation at the wall at the highest flowrate.

Supporting the mental health of children and youth of separating parents

PubMed Central

Clark, Brenda

2013-01-01

The rising international trend in the number of parents who separate or divorce is raising concerns about long-term consequences for child and youth well-being and adjustment to adulthood. Separation and divorce may increase risks for negative outcomes in physical, mental, educational and psychosocial well-being during childhood and later, as youth transition to adulthood. Most children of separated and divorced families do not have significant or diagnosable impairments. Family processes that have a positive mediating effect on child well-being after parental divorce or separation include improving the quality of parenting, improving the quality of parent–child relationships and controlling hostile conflict. Physicians can offer support and guidance to separating parents by helping them to identify risk factors, strengthen protective factors and enhance children’s capacity to cope with family changes. PMID:24421713

23 CFR 771.115 - Classes of actions.

Code of Federal Regulations, 2010 CFR

2010-04-01

... rail, light rail, commuter rail, automated guideway transit). (4) New construction or extension of a separate roadway for buses or high occupancy vehicles not located within an existing highway facility. (b...

23 CFR 771.115 - Classes of actions.

Code of Federal Regulations, 2012 CFR

2012-04-01

... rail, light rail, commuter rail, automated guideway transit). (4) New construction or extension of a separate roadway for buses or high occupancy vehicles not located within an existing highway facility. (b...

23 CFR 771.115 - Classes of actions.

Code of Federal Regulations, 2011 CFR

2011-04-01

... rail, light rail, commuter rail, automated guideway transit). (4) New construction or extension of a separate roadway for buses or high occupancy vehicles not located within an existing highway facility. (b...

Phase Transition between Black and Blue Phosphorenes: A Quantum Monte Carlo Study

NASA Astrophysics Data System (ADS)

Li, Lesheng; Yao, Yi; Reeves, Kyle; Kanai, Yosuke

Phase transition of the more common black phosphorene to blue phosphorene is of great interest because they are predicted to exhibit unique electronic and optical properties. However, these two phases are predicted to be separated by a rather large energy barrier. In this work, we study the transition pathway between black and blue phosphorenes by using the variable cell nudge elastic band method combined with density functional theory calculation. We show how diffusion quantum Monte Carlo method can be used for determining the energetics of the phase transition and demonstrate the use of two approaches for removing finite-size errors. Finally, we predict how applied stress can be used to control the energetic balance between these two different phases of phosphorene.

Clogging and jamming transitions in periodic obstacle arrays

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

Nguyen, Hong; Reichhardt, Charles; Olson Reichhardt, Cynthia Jane

2017-03-29

We numerically examine clogging transitions for bidisperse disks flowing through a two-dimensional periodic obstacle array. Here, we show that clogging is a probabilistic event that occurs through a transition from a homogeneous flowing state to a heterogeneous or phase-separated jammed state where the disks form dense connected clusters. The probability for clogging to occur during a fixed time increases with increasing particle packing and obstacle number. For driving at different angles with respect to the symmetry direction of the obstacle array, we show that certain directions have a higher clogging susceptibility. It is also possible to have a size-specific cloggingmore » transition in which one disk size becomes completely immobile while the other disk size continues to flow.« less

Localized superconductivity in the quantum-critical region of the disorder-driven superconductor-insulator transition in TiN thin films.

PubMed

Baturina, T I; Mironov, A Yu; Vinokur, V M; Baklanov, M R; Strunk, C

2007-12-21

We investigate low-temperature transport properties of thin TiN superconducting films in the vicinity of the disorder-driven superconductor-insulator transition. In a zero magnetic field, we find an extremely sharp separation between superconducting and insulating phases, evidencing a direct superconductor-insulator transition without an intermediate metallic phase. At moderate temperatures, in the insulating films we reveal thermally activated conductivity with the magnetic field-dependent activation energy. At very low temperatures, we observe a zero-conductivity state, which is destroyed at some depinning threshold voltage V{T}. These findings indicate the formation of a distinct collective state of the localized Cooper pairs in the critical region at both sides of the transition.