Mechanism of polymer drag reduction using a low-dimensional model.

PubMed

Roy, Anshuman; Morozov, Alexander; van Saarloos, Wim; Larson, Ronald G

2006-12-08

Using a retarded-motion expansion to describe the polymer stress, we derive a low-dimensional model to understand the effects of polymer elasticity on the self-sustaining process that maintains the coherent wavy streamwise vortical structures underlying wall-bounded turbulence. Our analysis shows that at small Weissenberg numbers, Wi, elasticity enhances the coherent structures. At higher Wi, however, polymer stresses suppress the streamwise vortices (rolls) by calming down the instability of the streaks that regenerates the rolls. We show that this behavior can be attributed to the nonmonotonic dependence of the biaxial extensional viscosity on Wi, and identify it as the key rheological property controlling drag reduction.

Shape-Reprogrammable Polymers: Encoding, Erasing, and Re-Encoding (Postprint)

DTIC Science & Technology

2014-11-01

printing , is a layer-by-layer technology for producing 3D objects directly from a digital model. While 3D printing allows the fabrication of increasingly...one linear shape-translation processes often increase rapidly with shape complexity. Additive manufacturing, also called three-dimensional ( 3D

Electrical and thermal transport in the quasiatomic limit of coupled Luttinger liquids

NASA Astrophysics Data System (ADS)

Szasz, Aaron; Ilan, Roni; Moore, Joel E.

2017-02-01

We introduce a new model for quasi-one-dimensional materials, motivated by intriguing but not yet well-understood experiments that have shown two-dimensional polymer films to be promising materials for thermoelectric devices. We consider a two-dimensional material consisting of many one-dimensional systems, each treated as a Luttinger liquid, with weak (incoherent) coupling between them. This approximation of strong interactions within each one-dimensional chain and weak coupling between them is the "quasiatomic limit." We find integral expressions for the (interchain) transport coefficients, including the electrical and thermal conductivities and the thermopower, and we extract their power law dependencies on temperature. Luttinger liquid physics is manifested in a violation of the Wiedemann-Franz law; the Lorenz number is larger than the Fermi liquid value by a factor between γ2 and γ4, where γ ≥1 is a measure of the electron-electron interaction strength in the system.

A numerical model for CO effect evaluation in HT-PEMFCs: Part 2 - Application to different membranes

NASA Astrophysics Data System (ADS)

Cozzolino, R.; Chiappini, D.; Tribioli, L.

2016-06-01

In this paper, a self-made numerical model of a high temperature polymer electrolyte membrane fuel cell is presented. In particular, we focus on the impact of CO poisoning on fuel cell performance and its influence on electrochemical modelling. More specifically, the aim of this work is to demonstrate the effectiveness of our zero-dimensional electrochemical model of HT-PEMFCs, by comparing numerical and experimental results, obtained from two different commercial membranes electrode assemblies: the first one is based on polybenzimidazole (PBI) doped with phosphoric acid, while the second one uses a PBI electrolyte with aromatic polyether polymers/copolymers bearing pyridine units, always doped with H3PO4. The analysis has been carried out considering both the effect of CO poisoning and operating temperature for the two membranes above mentioned.

Photophysics of single-walled carbon nanotubes: similarity with π-conjugated polymer

NASA Astrophysics Data System (ADS)

Zhao, Hongbo

2006-03-01

Coulomb electron-electron (e-e) interactions among the π-electrons have a strong effect on the energy spectra of semiconducting single-walled carbon nanotubes (S-SWCNTs), because of their quasi-one-dimensionality. The primary photoexcitations in S-SWCNTs as a consequence of e-e interactions are excitons, as opposed to free electrons and holes. There already exists a vast literature on excitons in π-conjugated polymers, the other class of carbon-based quasi-one-dimensional semiconductors. In order to seek guidance from this knowledge base, we have performed theoretical calculations of the excited state electronic structures, linear absorptions and excited state absorptions for ten different S-SWCNTs with a wide range in diameters, within the same correlated π-electron model that has previously been applied to π-conjugated polymers. We found remarkable similarities in the excitonic energy spectra and nonlinear optical properties of S-SWCNTs on the one hand, and π-conjugated polymers on the other. The ``essential states'' model of third-order optical nonlinearity, previously developed for π-conjugated polymers, applies also to S-SWCNTs (with minor modifications for chiral S-SWCNTs which lack center of inversion). Our theory is able to explain semiquantitatively the results of nonlinear spectroscopic measurements on both S-SWCNTs and π-conjugated polymers. For wide S-SWCNTs with diameters ranging from 0.8--1.0 nm, we calculate exciton binding energies of 0.3--0.4 eV, in strong agreement with the values predicted from the experiments. We also remark on the occurrence of dark excitons below the optical excitons in the S-SWCNTs, and the consequence thereof on the photoluminescence of these materials. H. Zhao, et al., cond-mat/0506097; J. W. Kennedy, et al., cond-mat/0505071. S. N. Dixit, D. Guo, and S. Mazumdar, Phys. Rev. B 43, R6781 (1991) H. Zhao and S. Mazumdar, Phys. Rev. Lett. 93, 157402 (2004).

Semiflexible macromolecules in quasi-one-dimensional confinement: Discrete versus continuous bond angles.

PubMed

Huang, Aiqun; Hsu, Hsiao-Ping; Bhattacharya, Aniket; Binder, Kurt

2015-12-28

The conformations of semiflexible polymers in two dimensions confined in a strip of width D are studied by computer simulations, investigating two different models for the mechanism by which chain stiffness is realized. One model (studied by molecular dynamics) is a bead-spring model in the continuum, where stiffness is controlled by a bond angle potential allowing for arbitrary bond angles. The other model (studied by Monte Carlo) is a self-avoiding walk chain on the square lattice, where only discrete bond angles (0° and ±90°) are possible, and the bond angle potential then controls the density of kinks along the chain contour. The first model is a crude description of DNA-like biopolymers, while the second model (roughly) describes synthetic polymers like alkane chains. It is first demonstrated that in the bulk the crossover from rods to self-avoiding walks for both models is very similar, when one studies average chain linear dimensions, transverse fluctuations, etc., despite their differences in local conformations. However, in quasi-one-dimensional confinement two significant differences between both models occur: (i) The persistence length (extracted from the average cosine of the bond angle) gets renormalized for the lattice model when D gets less than the bulk persistence length, while in the continuum model it stays unchanged. (ii) The monomer density near the repulsive walls for semiflexible polymers is compatible with a power law predicted for the Kratky-Porod model in the case of the bead-spring model, while for the lattice case it tends to a nonzero constant across the strip. However, for the density of chain ends, such a constant behavior seems to occur for both models, unlike the power law observed for flexible polymers. In the regime where the bulk persistence length ℓp is comparable to D, hairpin conformations are detected, and the chain linear dimensions are discussed in terms of a crossover from the Daoud/De Gennes "string of blobs"-picture to the flexible rod picture when D decreases and/or the chain stiffness increases. Introducing a suitable further coarse-graining of the chain contours of the continuum model, direct estimates for the deflection length and its distribution could be obtained.

One-dimensional Cu(II) coordination polymers containing C2h-symmetric 1,1':4',1''-terphenyl-3,3'-dicarboxylate linkers.

PubMed

Kim, Hyun Chul; Gu, Ja Min; Huh, Seong; Yo, Chul Hyun; Kim, Youngmee

2015-10-01

Two new one-dimensional Cu(II) coordination polymers (CPs) containing the C2h-symmetric terphenyl-based dicarboxylate linker 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), namely catena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(4)O,O':O'':O'''] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(2)O(3):O(3')] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu(II) ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

Photonic polymer-blend structures and method for making

DOEpatents

Barnes, Michael D.

2004-06-29

The present invention comprises the formation of photonic polymer-blend structures having tunable optical and mechanical properties. The photonic polymer-blend structures comprise monomer units of spherical microparticles of a polymer-blend material wherein the spherical microparticles have surfaces partially merged with one another in a robust inter-particle bond having a tunable inter-particle separation or bond length sequentially attached in a desired and programmable architecture. The photonic polymer-blend structures of the present invention can be linked by several hundred individual particles sequentially linked to form complex three-dimensional structures or highly ordered two-dimensional arrays of 3D columns with 2D spacing.

Ordered quasi-two-dimensional structure of nanoparticles in semiflexible ring polymer brushes under compression

NASA Astrophysics Data System (ADS)

Hua, Yunfeng; Deng, Zhenyu; Jiang, Yangwei; Zhang, Linxi

2017-06-01

Molecular dynamics simulations of a coarse-grained bead-spring model of ring polymer brushes under compression are presented. Flexible polymer brushes are always disordered during compression, whereas semiflexible polymer brushes tend to be ordered under sufficiently strong compression. Further, the polymer monomer density of the semiflexible polymer brush is very high near the brush surface, inducing a peak value of the free energy near the surface. Therefore, when nanoparticles are compressed in semiflexible ring polymer brushes, they tend to exhibit a closely packed single-layer structure between the brush surface and the impenetrable wall, and a quasi-two-dimensional ordered structure near the brush surface is formed under strong compression. These findings provide a new approach to designing responsive applications.

Outgassing and dimensional changes of polymer matrix composites in space

NASA Technical Reports Server (NTRS)

Tennyson, R. C.; Matthews, R.

1993-01-01

A thermal-vacuum outgassing model and test protocol for predicting outgassing times and dimensional changes for polymer matrix composites is described. Experimental results derived from a 'control' sample are used to provide the basis for analytical predictions to compare with the outgassing response of Long Duration Exposure Facility (LDEF) flight samples.

Novel Three-Dimensional Interphase Characterisation of Polymer Nanocomposites Using Nanoscaled Topography.

PubMed

Mousa, Mohanad; Dong, Yu

2018-06-19

Mechanical properties of polymer nanocomposites depend primarily on nanointerphases as transitional zones between nanoparticles and surrounding matrices. Due to the difficulty in the quantitative characterisation of nanointerphases, previous literatures generally deemed such interphases as one-dimensional uniform zones around nanoparticles by assumption for analytical or theoretical modelling. We hereby have demonstrated for the first time direct three-dimensional topography and physical measurement of nanophase mechanical properties between nanodimeter bamboo charcoals (NBCs) and poly (vinyl alcohol) (PVA) in polymer nanocomposites. Topographical features, nanomechanical properties and dimensions of nanointerphases were systematically determined via peak force quantitative nanomechanical tapping mode (PFQNM). Significantly different mechanical properties of nanointerphases were revealed as opposed to those of individual NBCs and PVA matrices. Non-uniform irregular three-dimensional structures and shapes of nanointerphases are manifested around individual NBCs, which can be greatly influenced by nanoparticle size and roughness, and nanoparticle dispersion and distribution. Elastic moduli of nanointerphases were experimentally determined in range from 25.32 ±3.4 to 66.3±3.2 GPa. Additionally, it is clearly shown that the interphase modulus strongly depends on interphase surface area SAInterphase and interphase volume VInterphase. Different NBC distribution patterns from fully to partially embedded nanoparticles are proven to yield a remarkable reduction in elastic moduli of nanointerphases. © 2018 IOP Publishing Ltd.

Polymer diffusion in the interphase between surface and solution.

PubMed

Weger, Lukas; Weidmann, Monika; Ali, Wael; Hildebrandt, Marcus; Gutmann, Jochen Stefan; Hoffmann-Jacobsen, Kerstin

2018-05-22

Total internal reflection fluorescence correlation spectroscopy (TIR-FCS) is applied to study the self-diffusion of polyethylene glycol solutions in the presence of weakly attractive interfaces. Glass coverslips modified with aminopropyl- and propyl-terminated silanes are used to study the influence of solid surfaces on polymer diffusion. A model of three phases of polymer diffusion allows to describe the experimental fluorescence autocorrelation functions. Besides the two-dimensional diffusion of adsorbed polymer on the substrate and three-dimensional free diffusion in bulk solution, a third diffusion time scale is observed with intermediate diffusion times. This retarded three-dimensional diffusion in solution is assigned to long range effects of solid surfaces on diffusional dynamics of polymers. The respective diffusion constants show Rouse scaling (D~N -1 ) indicating a screening of hydrodynamic interactions by the presence of the surface. Hence, the presented TIR-FCS method proves to be a valuable tool to investigate the effect of surfaces on polymer diffusion beyond the first adsorbed polymer layer on the 100 nm length scale.

Development of an Unstructured, Three-Dimensional Material Response Design Tool

NASA Technical Reports Server (NTRS)

Schulz, Joseph; Stern, Eric; Palmer, Grant; Muppidi, Suman; Schroeder, Olivia

2017-01-01

A preliminary verification and validation of a new material response model is presented. This model, Icarus, is intended to serve as a design tool for the thermal protection systems of re-entry vehicles. Currently, the capability of the model is limited to simulating the pyrolysis of a material as a result of the radiative and convective surface heating imposed on the material from the surrounding high enthalpy gas. Since the major focus behind the development of Icarus has been model extensibility, the hope is that additional physics can be quickly added. The extensibility is critical since thermal protection systems are becoming increasing complex, e.g. woven carbon polymers. Additionally, as a three-dimensional, unstructured, finite-volume model, Icarus is capable of modeling complex geometries as well as multi-dimensional physics, which have been shown to be important in some scenarios and are not captured by one-dimensional models. In this paper, the mathematical and numerical formulation is presented followed by a discussion of the software architecture and some preliminary verification and validation studies.

Graphical Representations and Cluster Algorithms for Ice Rule Vertex Models.

NASA Astrophysics Data System (ADS)

Shtengel, Kirill; Chayes, L.

2002-03-01

We introduce a new class of polymer models which is closely related to loop models, recently a topic of intensive studies. These particular models arise as graphical representations for ice-rule vertex models. The associated cluster algorithms provide a unification and generalisation of most of the existing algorithms. For many lattices, percolation in the polymer models evidently indicates first order phase transitions in the vertex models. Critical phases can be understood as being susceptible to colour symmetry breaking in the polymer models. The analysis includes, but is certainly not limited to the square lattice six-vertex model. In particular, analytic criteria can be found for low temperature phases in other even coordinated 2D lattices such as the triangular lattice, or higher dimensional lattices such as the hyper-cubic lattices of arbitrary dimensionality. Finally, our approach can be generalised to the vertex models that do not obey the ice rule, such as the eight-vertex model.

Translocation of a polymer through a nanopore across a viscosity gradient.

PubMed

de Haan, Hendrick W; Slater, Gary W

2013-04-01

The translocation of a polymer through a pore in a membrane separating fluids of different viscosities is studied via several computational approaches. Starting with the polymer halfway, we find that as a viscosity difference across the pore is introduced, translocation will predominately occur towards one side of the membrane. These results suggest an intrinsic pumping mechanism for translocation across cell walls which could arise whenever the fluid across the membrane is inhomogeneous. Somewhat surprisingly, the sign of the preferred direction of translocation is found to be strongly dependent on the simulation algorithm: for Langevin dynamics (LD) simulations, a bias towards the low viscosity side is found while for Brownian dynamics (BD), a bias towards the high viscosity is found. Examining the translocation dynamics in detail across a wide range of viscosity gradients and developing a simple force model to estimate the magnitude of the bias, the LD results are demonstrated to be more physically realistic. The LD results are also compared to those generated from a simple, one-dimensional random walk model of translocation to investigate the role of the internal degrees of freedom of the polymer and the entropic barrier. To conclude, the scaling of the results across different polymer lengths demonstrates the saturation of the directional preference with polymer length and the nontrivial location of the maximum in the exponent corresponding to the scaling of the translocation time with polymer length.

Fabrication routes for one-dimensional nanostructures via block copolymers

NASA Astrophysics Data System (ADS)

Tharmavaram, Maithri; Rawtani, Deepak; Pandey, Gaurav

2017-05-01

Nanotechnology is the field which deals with fabrication of materials with dimensions in the nanometer range by manipulating atoms and molecules. Various synthesis routes exist for the one, two and three dimensional nanostructures. Recent advancements in nanotechnology have enabled the usage of block copolymers for the synthesis of such nanostructures. Block copolymers are versatile polymers with unique properties and come in many types and shapes. Their properties are highly dependent on the blocks of the copolymers, thus allowing easy tunability of its properties. This review briefly focusses on the use of block copolymers for synthesizing one-dimensional nanostructures especially nanowires, nanorods, nanoribbons and nanofibers. Template based, lithographic, and solution based approaches are common approaches in the synthesis of nanowires, nanorods, nanoribbons, and nanofibers. Synthesis of metal, metal oxides, metal oxalates, polymer, and graphene one dimensional nanostructures using block copolymers have been discussed as well.

Self-Assembly of Emulsion Droplets into Polymer Chains

NASA Astrophysics Data System (ADS)

Bargteil, Dylan; McMullen, Angus; Brujic, Jasna

We experimentally investigate `beads-on-a-string' models of polymers using the spontaneous assembly of emulsion droplets into linear chains. Droplets functionalized with surface-mobile DNA allow for programmable 'monomers' through which we can influence the three-dimensional structure of the assembled 'polymer'. Such model polymers can be used to study conformational changes of polypeptides and the principles governing protein folding. In our system, we find that droplets bind via complementary DNA strands that are recruited into adhesion patches. Recruitment is driven by the DNA hybridization energy, and is limited by the energy cost of surface deformation and the entropy loss of the mobile linkers, yielding adhesion patches of a characteristic size with a given number of linkers. By tuning the initial surface coverage of linkers, we control valency between the droplets to create linear or branched polymer chains. We additionally control the flexibility of the model polymers by varying the salt concentration and study their dynamics between extended and collapsed states. This system opens the possibility of programming stable three-dimensional structures, such as those found within folded proteins.

Fabrication of multilayered conductive polymer structures via selective visible light photopolymerization

NASA Astrophysics Data System (ADS)

Cullen, Andrew T.; Price, Aaron D.

2017-04-01

Electropolymerization of pyrrole is commonly employed to fabricate intrinsically conductive polymer films that exhibit desirable electromechanical properties. Due to their monolithic nature, electroactive polypyrrole films produced via this process are typically limited to simple linear or bending actuation modes, which has hindered their application in complex actuation tasks. This initiative aims to develop the specialized fabrication methods and polymer formulations required to realize three-dimensional conductive polymer structures capable of more elaborate actuation modes. Our group has previously reported the application of the digital light processing additive manufacturing process for the fabrication of three-dimensional conductive polymer structures using ultraviolet radiation. In this investigation, we further expand upon this initial work and present an improved polymer formulation designed for digital light processing additive manufacturing using visible light. This technology enables the design of novel electroactive polymer sensors and actuators with enhanced capabilities and brings us one step closer to realizing more advanced electroactive polymer enabled devices.

Three-Dimensional (3D) Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling.

PubMed

Fafenrot, Susanna; Grimmelsmann, Nils; Wortmann, Martin; Ehrmann, Andrea

2017-10-19

Fused deposition modeling (FDM) is a three-dimensional (3D) printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid) (PLA) printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength.

Three-Dimensional (3D) Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling

PubMed Central

Fafenrot, Susanna; Grimmelsmann, Nils; Wortmann, Martin

2017-01-01

Fused deposition modeling (FDM) is a three-dimensional (3D) printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid) (PLA) printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength. PMID:29048347

Dimensional modulation and magnetic properties of triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates

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

Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin

2014-04-01

Five new metal–organic coordination polymers ([Cu{sub 3}(μ{sub 2}-OH){sub 2}(atrz){sub 2}(nph){sub 2}(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (1), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)]·2H{sub 2}O){sub n} (2), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)(H{sub 2}O)]·H{sub 2}O){sub n} (3), [Cu(dth){sub 0.5}(nph)(H{sub 2}O)]{sub n} (4) and [Cu(dth)(Hnip){sub 2}]{sub n} (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H{sub 2}nph=3-nitrophthalic acid, 1,2,4-H{sub 3}btc=1,2,4-benzenetricarboxylic acid and H{sub 2}nip=5-nitroisophthalic acid] were hydrothermally synthesized and structurally characterized. Polymer 1 shows a one-dimensional (1D) chain. Polymers 2 and 3 exhibit similar tetranuclear Cu{sup II}{sub 4} cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 4{sup 12}·6{sup 3}-pcu topology. Polymer 5 displays a 3D frameworkmore » with a 4{sup 4}·6{sup 10}·8-mab topology. The magnetic properties of 1–4 were investigated. - Graphical abstract: Five triazole-based copper(II) polymers modulated by polycarboxylates were synthesized. Bis-triazole-bis-amide ligand and polycarboxylates play important roles in tuning dimensionality of polymers. Magnetic properties of polymers were investigated. - Highlights: • Five triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates were obtained. • The aromatic polycarboxylates have an important influence on the dimensionality of five polymers. • The magnetic properties of four polymers were investigated.« less

Mechanical transduction via a single soft polymer

NASA Astrophysics Data System (ADS)

Hou, Ruizheng; Wang, Nan; Bao, Weizhu; Wang, Zhisong

2018-04-01

Molecular machines from biology and nanotechnology often depend on soft structures to perform mechanical functions, but the underlying mechanisms and advantages or disadvantages over rigid structures are not fully understood. We report here a rigorous study of mechanical transduction along a single soft polymer based on exact solutions to the realistic three-dimensional wormlike-chain model and augmented with analytical relations derived from simpler polymer models. The results reveal surprisingly that a soft polymer with vanishingly small persistence length below a single chemical bond still transduces biased displacement and mechanical work up to practically significant amounts. This "soft" approach possesses unique advantages over the conventional wisdom of rigidity-based transduction, and potentially leads to a unified mechanism for effective allosterylike transduction and relay of mechanical actions, information, control, and molecules from one position to another in molecular devices and motors. This study also identifies an entropy limit unique to the soft transduction, and thereby suggests a possibility of detecting higher efficiency for kinesin motor and mutants in future experiments.

Modeling Woven Polymer Matrix Composites with MAC/GMC

NASA Technical Reports Server (NTRS)

Bednarcyk, Brett A.; Arnold, Steven M. (Technical Monitor)

2000-01-01

NASA's Micromechanics Analysis Code with Generalized Method of Cells (MAC/GMC) is used to predict the elastic properties of plain weave polymer matrix composites (PMCs). The traditional one step three-dimensional homogertization procedure that has been used in conjunction with MAC/GMC for modeling woven composites in the past is inaccurate due to the lack of shear coupling inherent to the model. However, by performing a two step homogenization procedure in which the woven composite repeating unit cell is homogenized independently in the through-thickness direction prior to homogenization in the plane of the weave, MAC/GMC can now accurately model woven PMCs. This two step procedure is outlined and implemented, and predictions are compared with results from the traditional one step approach and other models and experiments from the literature. Full coupling of this two step technique with MAC/ GMC will result in a widely applicable, efficient, and accurate tool for the design and analysis of woven composite materials and structures.

Influence of macromolecular architecture on necking in polymer extrusion film casting process

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

Pol, Harshawardhan; Banik, Sourya; Azad, Lal Busher

2015-05-22

Extrusion film casting (EFC) is an important polymer processing technique that is used to produce several thousand tons of polymer films/coatings on an industrial scale. In this research, we are interested in understanding quantitatively how macromolecular chain architecture (for example long chain branching (LCB) or molecular weight distribution (MWD or PDI)) influences the necking and thickness distribution of extrusion cast films. We have used different polymer resins of linear and branched molecular architecture to produce extrusion cast films under controlled experimental conditions. The necking profiles of the films were imaged and the velocity profiles during EFC were monitored using particlemore » tracking velocimetry (PTV) technique. Additionally, the temperature profiles were captured using an IR thermography and thickness profiles were calculated. The experimental results are compared with predictions of one-dimensional flow model of Silagy et al{sup 1} wherein the polymer resin rheology is modeled using molecular constitutive equations such as the Rolie-Poly (RP) and extended Pom Pom (XPP). We demonstrate that the 1-D flow model containing the molecular constitutive equations provides new insights into the role of macromolecular chain architecture on film necking.{sup 1}D. Silagy, Y. Demay, and J-F. Agassant, Polym. Eng. Sci., 36, 2614 (1996)« less

Translocation of a Polymer Chain across a Nanopore: A Brownian Dynamics Simulation Study

NASA Technical Reports Server (NTRS)

Tian, Pu; Smith, Grant D.

2003-01-01

We carried out Brownian dynamics simulation studies of the translocation of single polymer chains across a nanosized pore under the driving of an applied field (chemical potential gradient). The translocation process can be either dominated by the entropic barrier resulted from restricted motion of flexible polymer chains or by applied forces (or chemical gradient across the wall), we focused on the latter case in our studies. Calculation of radius of gyrations at the two opposite sides of the wall shows that the polymer chains are not in equilibrium during the translocation process. Despite this fact, our results show that the one-dimensional diffusion and the nucleation model provide an excellent description of the dependence of average translocation time on the chemical potential gradients, the polymer chain length and the solvent viscosity. In good agreement with experimental results and theoretical predictions, the translocation time distribution of our simple model shows strong non-Gaussian characteristics. It is observed that even for this simple tubelike pore geometry, more than one peak of translocation time distribution can be generated for proper pore diameter and applied field strengths. Both repulsive Weeks-Chandler-Anderson and attractive Lennard-Jones polymer-nanopore interaction were studied, attraction facilitates the translocation process by shortening the total translocation time and dramatically improve the capturing of polymer chain. The width of the translocation time distribution was found to decrease with increasing temperature, increasing field strength, and decreasing pore diameter.

Recent Progress on Ferroelectric Polymer-Based Nanocomposites for High Energy Density Capacitors: Synthesis, Dielectric Properties, and Future Aspects.

PubMed

Prateek; Thakur, Vijay Kumar; Gupta, Raju Kumar

2016-04-13

Dielectric polymer nanocomposites are rapidly emerging as novel materials for a number of advanced engineering applications. In this Review, we present a comprehensive review of the use of ferroelectric polymers, especially PVDF and PVDF-based copolymers/blends as potential components in dielectric nanocomposite materials for high energy density capacitor applications. Various parameters like dielectric constant, dielectric loss, breakdown strength, energy density, and flexibility of the polymer nanocomposites have been thoroughly investigated. Fillers with different shapes have been found to cause significant variation in the physical and electrical properties. Generally, one-dimensional and two-dimensional nanofillers with large aspect ratios provide enhanced flexibility versus zero-dimensional fillers. Surface modification of nanomaterials as well as polymers adds flavor to the dielectric properties of the resulting nanocomposites. Nowadays, three-phase nanocomposites with either combination of fillers or polymer matrix help in further improving the dielectric properties as compared to two-phase nanocomposites. Recent research has been focused on altering the dielectric properties of different materials while also maintaining their superior flexibility. Flexible polymer nanocomposites are the best candidates for application in various fields. However, certain challenges still present, which can be solved only by extensive research in this field.

Time-Domain Ab Initio Analysis of Excitation Dynamics in a Quantum Dot/Polymer Hybrid: Atomistic Description Rationalizes Experiment.

PubMed

Long, Run; Prezhdo, Oleg V

2015-07-08

Hybrid organic/inorganic polymer/quantum dot (QD) solar cells are an attractive alternative to the traditional cells. The original, simple models postulate that one-dimensional polymers have continuous energy levels, while zero-dimensional QDs exhibit atom-like electronic structure. A realistic, atomistic viewpoint provides an alternative description. Electronic states in polymers are molecule-like: finite in size and discrete in energy. QDs are composed of many atoms and have high, bulk-like densities of states. We employ ab initio time-domain simulation to model the experimentally observed ultrafast photoinduced dynamics in a QD/polymer hybrid and show that an atomistic description is essential for understanding the time-resolved experimental data. Both electron and hole transfers across the interface exhibit subpicosecond time scales. The interfacial processes are fast due to strong electronic donor-acceptor, as evidenced by the densities of the photoexcited states which are delocalized between the donor and the acceptor. The nonadiabatic charge-phonon coupling is also strong, especially in the polymer, resulting in rapid energy losses. The electron transfer from the polymer is notably faster than the hole transfer from the QD, due to a significantly higher density of acceptor states. The stronger molecule-like electronic and charge-phonon coupling in the polymer rationalizes why the electron-hole recombination inside the polymer is several orders of magnitude faster than in the QD. As a result, experiments exhibit multiple transfer times for the long-lived hole inside the QD, ranging from subpicoseconds to nanoseconds. In contrast, transfer of the short-lived electron inside the polymer does not occur beyond the first picosecond. The energy lost by the hole on its transit into the polymer is accommodated by polymer's high-frequency vibrations. The energy lost by the electron injected into the QD is accommodated primarily by much lower-frequency collective and QD modes. The electron dynamics is exponential, whereas evolution of the injected hole through the low density manifold of states of the polymer is highly nonexponential. The time scale of the electron-hole recombination at the interface is intermediate between those in pristine polymer and QD and is closer to that in the polymer. The detailed atomistic insights into the photoinduced charge and energy dynamics at the polymer/QD interface provide valuable guidelines for optimization of solar light harvesting and photovoltaic efficiency in modern nanoscale materials.

Molecular weaving via surface-templated epitaxy of crystalline coordination networks.

NASA Astrophysics Data System (ADS)

Wang, Zhengbang; Błaszczyk, Alfred; Fuhr, Olaf; Heissler, Stefan; Wöll, Christof; Mayor, Marcel

2017-02-01

One of the dream reactions in polymer chemistry is the bottom-up, self-assembled synthesis of polymer fabrics, with interwoven, one-dimensional fibres of monomolecular thickness forming planar pieces of textiles. We have made a major step towards realizing this goal by assembling sophisticated, quadritopic linkers into surface-mounted metal-organic frameworks. By sandwiching these quadritopic linkers between sacrificial metal-organic framework thin films, we obtained multi-heteroepitaxial, crystalline systems. In a next step, Glaser-Hay coupling of triple bonds in the quadritopic linkers yields linear, interwoven polymer chains. X-ray diffraction studies revealed that this topochemical reaction leaves the MOF backbone completely intact. After removing the metal ions, the textile sheets can be transferred onto different supports and imaged using scanning electron microscopy and atomic-force microscopy. The individual polymer strands forming the two-dimensional textiles have lengths on the order of 200 nm, as evidenced by atomic-force microscopy images recorded from the disassembled textiles.

Syntheses, structures and properties of four Cd(II) coordination polymers induced by the pH regulator

NASA Astrophysics Data System (ADS)

Xu, Yun; Ding, Fang; Liu, Dong; Yang, Pei-Pei; Zhu, Li-Li

2018-03-01

Four new coordination polymers [Cd2(CHDC)2(APYZ)(H2O)2](H2O) (1), [Cd(HCHDC)2(APYZ) (H2O)] (2), [Cd2(CHDC)2(PYZ)(H2O)2](H2O) (3), and [Cd(HCHDC)2(PYZ)(H2O)] (4) (H2CHDC = 1,4-cyclohexanedicarboxylic acid, APYZ = 2-aminopyrazine, PYZ = pyrazine) have been synthesized under the hydrothermal conditions by changing the pH regulator and the N-containing ligands. The pH regulator impacted on the degree of deprotonation of the 1,4-cyclohexanedicarboxylic acid ligand and resulted in the formation of the two pairs of different networks. Polymers 1 and 3 crystallize in monoclinic, space group P21/c, exhibit two dimensional 63 net, which further formed three-dimensional supramolecular structure by the Csbnd H⋯O hydrogen bond interactions. While polymers 2 and 4 possess one dimensional chain structures and further link into two dimensional layered supramolecular structures by intermolecular hydrogen bonding interactions. From all three conformers of H2CHDC, e,a-cis is consistently present in the Cd coordination polymers. Furthermore, photoluminescence properties of four polymers are also investigated, the luminescent intensity of polymer 1 (or 2) with amino group in pyrazine is dramatically stronger than that of the similar structure of polymer 3 (or 4) without amino group in pyrazine, the results shown that the presence of the amino group from 2-aminopyrazine play a key role in increasing the luminescence properties.

Durable polymer-aerogel based superhydrophobic coatings, a composite material

DOEpatents

Kissel, David J; Brinker, Charles Jeffrey

2014-03-04

Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140.degree. and a contact angle hysteresis of less than about 1.degree.. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

Durable polymer-aerogel based superhydrophobic coatings: a composite material

DOEpatents

Kissel, David J.; Brinker, Charles Jeffrey

2016-02-02

Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140.degree. and a contact angle hysteresis of less than about 1.degree.. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

Visualization of Au Nanoparticles Buried in a Polymer Matrix by Scanning Thermal Noise Microscopy.

PubMed

Yao, Atsushi; Kobayashi, Kei; Nosaka, Shunta; Kimura, Kuniko; Yamada, Hirofumi

2017-02-17

Several researchers have recently demonstrated visualization of subsurface features with a nanometer-scale resolution using various imaging schemes based on atomic force microscopy. Since all these subsurface imaging techniques require excitation of the oscillation of the cantilever and/or sample surface, it has been difficult to identify a key imaging mechanism. Here we demonstrate visualization of Au nanoparticles buried 300 nm into a polymer matrix by measurement of the thermal noise spectrum of a microcantilever with a tip in contact to the polymer surface. We show that the subsurface Au nanoparticles are detected as the variation in the contact stiffness and damping reflecting the viscoelastic properties of the polymer surface. The variation in the contact stiffness well agrees with the effective stiffness of a simple one-dimensional model, which is consistent with the fact that the maximum depth range of the technique is far beyond the extent of the contact stress field.

From particle condensation to polymer aggregation

NASA Astrophysics Data System (ADS)

Janke, Wolfhard; Zierenberg, Johannes

2018-01-01

We draw an analogy between droplet formation in dilute particle and polymer systems. Our arguments are based on finite-size scaling results from studies of a two-dimensional lattice gas to three-dimensional bead-spring polymers. To set the results in perspective, we compare with in part rigorous theoretical scaling laws for canonical condensation in a supersaturated gas at fixed temperature, and derive corresponding scaling predictions for an undercooled gas at fixed density. The latter allows one to efficiently employ parallel multicanonical simulations and to reach previously not accessible scaling regimes. While the asymptotic scaling can not be observed for the comparably small polymer system sizes, they demonstrate an intermediate scaling regime also observable for particle condensation. Altogether, our extensive results from computer simulations provide clear evidence for the close analogy between particle condensation and polymer aggregation in dilute systems.

Fast Three-Dimensional Method of Modeling Atomic Oxygen Undercutting of Protected Polymers

NASA Technical Reports Server (NTRS)

Snyder, Aaron; Banks, Bruce A.

2002-01-01

A method is presented to model atomic oxygen erosion of protected polymers in low Earth orbit (LEO). Undercutting of protected polymers by atomic oxygen occurs in LEO due to the presence of scratch, crack or pin-window defects in the protective coatings. As a means of providing a better understanding of undercutting processes, a fast method of modeling atomic-oxygen undercutting of protected polymers has been developed. Current simulation methods often rely on computationally expensive ray-tracing procedures to track the surface-to-surface movement of individual "atoms." The method introduced in this paper replaces slow individual particle approaches by substituting a model that utilizes both a geometric configuration-factor technique, which governs the diffuse transport of atoms between surfaces, and an efficient telescoping series algorithm, which rapidly integrates the cumulative effects stemming from the numerous atomic oxygen events occurring at the surfaces of an undercut cavity. This new method facilitates the systematic study of three-dimensional undercutting by allowing rapid simulations to be made over a wide range of erosion parameters.

A molecular design principle of lyotropic liquid-crystalline conjugated polymers with directed alignment capability for plastic electronics

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

Kim, Bong-Gi; Jeong, Eun Jeong; Chung, Jong Won

Conjugated polymers with a one-dimensional p-orbital overlap exhibit optoelectronic anisotropy. Their unique anisotropic properties can be fully realized in device applications only when the conjugated chains are aligned. Here, we report a molecular design principle of conjugated polymers to achieve concentration-regulated chain planarization, self-assembly, liquid-crystal-like good mobility and non-interdigitated side chains. As a consequence of these intra- and intermolecular attributes, chain alignment along an applied flow field occurs. This liquid-crystalline conjugated polymer was realized by incorporating intramolecular sulphur–fluorine interactions and bulky side chains linked to a tetrahedral carbon having a large form factor. By optimizing the polymer concentration and themore » flow field, we could achieve a high dichroic ratio of 16.67 in emission from conducting conjugated polymer films. Two-dimensional grazing-incidence X-ray diffraction was performed to analyse a well-defined conjugated polymer alignment. Thin-film transistors built on highly aligned conjugated polymer films showed more than three orders of magnitude faster carrier mobility along the conjugated polymer alignment direction than the perpendicular direction.« less

Universality class of the two-dimensional polymer collapse transition

NASA Astrophysics Data System (ADS)

Nahum, Adam

2016-05-01

The nature of the θ point for a polymer in two dimensions has long been debated, with a variety of candidates put forward for the critical exponents. This includes those derived by Duplantier and Saleur for an exactly solvable model. We use a representation of the problem via the CPN -1σ model in the limit N →1 to determine the stability of this critical point. First we prove that the Duplantier-Saleur (DS) critical exponents are robust, so long as the polymer does not cross itself: They can arise in a generic lattice model and do not require fine-tuning. This resolves a longstanding theoretical question. We also address an apparent paradox: Two different lattice models, apparently both in the DS universality class, show different numbers of relevant perturbations, apparently leading to contradictory conclusions about the stability of the DS exponents. We explain this in terms of subtle differences between the two models, one of which is fine-tuned (and not strictly in the DS universality class). Next we allow the polymer to cross itself, as appropriate, e.g., to the quasi-two-dimensional case. This introduces an additional independent relevant perturbation, so we do not expect the DS exponents to apply. The exponents in the case with crossings will be those of the generic tricritical O (n ) model at n =0 and different from the case without crossings. We also discuss interesting features of the operator content of the CPN -1 model. Simple geometrical arguments show that two operators in this field theory, with very different symmetry properties, have the same scaling dimension for any value of N (or, equivalently, any value of the loop fugacity). Also we argue that for any value of N the CPN -1 model has a marginal odd-parity operator that is related to the winding angle.

A one-dimensional nickel(II) coordination polymer containing 2,6-dipicolinate and dipyrido[3,2-a:2',3'-c]phenazine.

PubMed

Ma, Yi; Zhang, Li-Tian; Wang, Xiao-Fang; He, Yong-Ke; Han, Zheng-Bo

2007-12-01

A new coordination polymer, catena-poly[[(dipyrido[3,2-a:2',3'-c]phenazine-kappa(2)N,N')nickel(II)]-mu-2,6-dipicolinato-kappa(4)O(2),N,O(6):O(2')], [Ni(C7H3NO4)(C18H10N4)]n, exhibits a one-dimensional structure in which 2,6-dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one Ni(II) center, one dipyrido[3,2-a:2',3'-c]phenazine ligand and one 2,6-dipicolinate ligand. Each Ni(II) center is six-coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2-a:2',3'-c]phenazine ligand and two different 2,6-dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by pi-pi stacking interactions and weak interactions to form a three-dimensional supramolecular network.

Co-assembly of Zn(SPh){sub 2} and organic linkers into helical and zig-zag polymer chains

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

Liu Yi; Yu Lingmin; Loo, Say Chye Joachim

2012-07-15

Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (EG=ethylene glycol) (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized under solvothermal conditions at 150 Degree-Sign C or room temperature by the co-assembly of Zn(SPh){sub 2} and organic linkers such as 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPyTA) and 1,3-bis(trans-4-pyridylvinyl)benzene (BPyVB). X-ray crystallography study reveals that both polymers 1 and 2 crystallize in space group P2{sub 1}/c of the monoclinic system. The solid-state UV-vis absorption spectra show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up tomore » 110 Degree-Sign C and 210 Degree-Sign C. - Graphical abstract: Two novel one-dimensional coordination polymers, single helicate [Zn(SPh){sub 2}(TPyTA)(EG)]{sub n} (1) and zig-zag structure [Zn(SPh){sub 2}(BPyVB)]{sub n} (2), were synthesized. Solid-state UV-vis absorptions show that 1 and 2 have maxium absorption onsets at 400 nm and 420 nm, respectively. TGA analysis indicates that 1 and 2 are stable up to 110 Degree-Sign C and 210 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Two novel one-dimensional coordination polymers have been synthesized. Black-Right-Pointing-Pointer TPyTA results in helical structures in 1 while BPyVB leads to zig-zag chains in 2. Black-Right-Pointing-Pointer Solid-state UV-vis absorption spectra and TGA analysis of the title polymers were studied.« less

Bloch oscillations in organic and inorganic polymers

NASA Astrophysics Data System (ADS)

Ribeiro, Luiz Antonio; Ferreira da Cunha, Wiliam; de Almeida Fonseca, Antonio Luciano; e Silva, Geraldo Magela

2017-04-01

The transport of polarons above the mobility threshold in organic and inorganic polymers is theoretically investigated in the framework of a one-dimensional tight-binding model that includes lattice relaxation. The computational approach is based on parameters for which the model Hamiltonian suitably describes different polymer lattices in the presence of external electric fields. Our findings show that, above critical field strengths, a dissociated polaron moves through the polymer lattice as a free electron performing Bloch oscillations. These critical electric fields are considerably smaller for inorganic lattices in comparison to organic polymers. Interestingly, for inorganic lattices, the free electron propagates preserving charge and spin densities' localization which is a characteristic of a static polaron. Moreover, in the turning points of the spatial Bloch oscillations, transient polaron levels are formed inside the band gap, thus generating a fully characterized polaron structure. For the organic case, on the other hand, no polaron signature is observed: neither in the shape of the distortion—those polaron profile signatures are absent—nor in the energy levels—as no such polaron levels are formed during the simulation. These results solve controversial aspects concerning Bloch oscillations recently reported in the literature and may enlighten the understanding about the charge transport mechanism in polymers above their mobility edge.

A novel model of photothermal diffusion (PTD) for polymer nano-composite semiconducting of thin circular plate

NASA Astrophysics Data System (ADS)

Lotfy, Kh.

2018-05-01

In this article, theoretical discussions for a novel mathematical-physical Photothermal diffusion (PTD) model in the generalized thermoelasticity theory with photothermal processes and chemical action are introduced. The mean idea of this model depends on the interaction between quasi-particles (plasma waves) that depends on the kind of the used materials, the mechanical forces acting on the surface, the generalized thermo and mass diffusion (due to coupling of temperature fields with thermal waves and chemical potential) and the elastic waves. The one dimensional Laplace transforms is used to obtain the exact solution for some physical and chemical quantities for a thin circular plate of a semiconducting polymer nanocomposite such as silicon (Si). New variables are deduced and discussed. The obtained results of the physical quantities are presented analytically and illustrated graphically with some important applications.

Molecular Simulation Evaluation of Macromolecular Transport through Nanofiltration Membranes

NASA Astrophysics Data System (ADS)

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

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

Molecular weaving via surface-templated epitaxy of crystalline coordination networks.

PubMed Central

Wang, Zhengbang; Błaszczyk, Alfred; Fuhr, Olaf; Heissler, Stefan; Wöll, Christof; Mayor, Marcel

2017-01-01

One of the dream reactions in polymer chemistry is the bottom-up, self-assembled synthesis of polymer fabrics, with interwoven, one-dimensional fibres of monomolecular thickness forming planar pieces of textiles. We have made a major step towards realizing this goal by assembling sophisticated, quadritopic linkers into surface-mounted metal-organic frameworks. By sandwiching these quadritopic linkers between sacrificial metal-organic framework thin films, we obtained multi-heteroepitaxial, crystalline systems. In a next step, Glaser–Hay coupling of triple bonds in the quadritopic linkers yields linear, interwoven polymer chains. X-ray diffraction studies revealed that this topochemical reaction leaves the MOF backbone completely intact. After removing the metal ions, the textile sheets can be transferred onto different supports and imaged using scanning electron microscopy and atomic-force microscopy. The individual polymer strands forming the two-dimensional textiles have lengths on the order of 200 nm, as evidenced by atomic-force microscopy images recorded from the disassembled textiles. PMID:28198388

Influence of molecular designs on polaronic and vibrational transitions in a conjugated push-pull copolymer

NASA Astrophysics Data System (ADS)

Cobet, Christoph; Gasiorowski, Jacek; Menon, Reghu; Hingerl, Kurt; Schlager, Stefanie; White, Matthew S.; Neugebauer, Helmut; Sariciftci, N. Serdar; Stadler, Philipp

2016-10-01

Electron-phonon interactions of free charge-carriers in doped pi-conjugated polymers are conceptually described by 1-dimensional (1D) delocalization. Thereby, polaronic transitions fit the 1D-Froehlich model in quasi-confined chains. However, recent developments in conjugated polymers have diversified the backbones to become elaborate heterocylcic macromolecules. Their complexity makes it difficult to investigate the electron-phonon coupling. In this work we resolve the electron-phonon interactions in the ground and doped state in a complex push-pull polymer. We focus on the polaronic transitions using in-situ spectroscopy to work out the differences between single-unit and push-pull systems to obtain the desired structural- electronic correlations in the doped state. We apply the classic 1D-Froehlich model to generate optical model fits. Interestingly, we find the 1D-approach in push-pull polarons in agreement to the model, pointing at the strong 1D-character and plain electronic structure of the push-pull structure. In contrast, polarons in the single-unit polymer emerge to a multi- dimensional problem difficult to resolve due to their anisotropy. Thus, we report an enhancement of the 1D-character by the push-pull concept in the doped state - an important view in light of the main purpose of push-pull polymers for photovoltaic devices.

Liquid water breakthrough location distances on a gas diffusion layer of polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Yu, Junliang; Froning, Dieter; Reimer, Uwe; Lehnert, Werner

2018-06-01

The lattice Boltzmann method is adopted to simulate the three dimensional dynamic process of liquid water breaking through the gas diffusion layer (GDL) in the polymer electrolyte membrane fuel cell. 22 micro-structures of Toray GDL are built based on a stochastic geometry model. It is found that more than one breakthrough locations are formed randomly on the GDL surface. Breakthrough location distance (BLD) are analyzed statistically in two ways. The distribution is evaluated statistically by the Lilliefors test. It is concluded that the BLD can be described by the normal distribution with certain statistic characteristics. Information of the shortest neighbor breakthrough location distance can be the input modeling setups on the cell-scale simulations in the field of fuel cell simulation.

Conductivity fluctuations in polymer's networks

NASA Astrophysics Data System (ADS)

Samukhin, A. N.; Prigodin, V. N.; Jastrabík, L.

1998-01-01

A Polymer network is treated as an anisotropic fractal with fractional dimensionality D = 1 + ε close to one. Percolation model on such a fractal is studied. Using real space renormalization group approach of Migdal and Kadanoff, we find the threshold value and all the critical exponents in the percolation model to be strongly nonanalytic functions of ε, e.g. the critical exponent of the conductivity was obtained to be ε-2 exp (-1 - 1/ε). The main part of the finite-size conductivities distribution function at the threshold was found to be universal if expressed in terms of the fluctuating variable which is proportional to a large power of the conductivity, but with ε-dependent low-conductivity cut-off. Its reduced central momenta are of the order of e -1/ε up to a very high order.

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

[Using Molecular Simulations to Understand Complex Nanoscale Dynamic Phenomena in Polymer Solutions

NASA Technical Reports Server (NTRS)

Smith, Grant

2004-01-01

The first half of the project concentrated on molecular simulation studies of the translocation of model molecules for single-stranded DNA through a nanosized pore. This has resulted in the publication, Translocation of a polymer chain across a nanopore: A Brownian dynamics simulation study, by Pu Tian and Grant D. Smith, JOURNAL OF CHEMICAL PHYSICS VOLUME 119, NUMBER 21 1 DECEMBER 2003, which is attached to this report. In this work we carried out Brownian dynamics simulation studies of the translocation of single polymer chains across a nanosized pore under the driving of an applied field (chemical potential gradient) designed to mimic an electrostatic field. The translocation process can be either dominated by the entropic barrier resulted from restricted motion of flexible polymer chains or by applied forces (or chemical gradient). We focused on the latter case in our studies. Calculation of radius of gyration of the translocating chain at the two opposite sides of the wall shows that the polymer chains are not in equilibrium during the translocation process. Despite this fact, our results show that the one-dimensional diffusion and the nucleation model provide an excellent description of the dependence of average translocation time on the chemical potential gradients, the polymer chain length and the solvent viscosity. In good agreement with experimental results and theoretical predictions, the translocation time distribution of our simple model shows strong non-Gaussian characteristics. It is observed that even for this simple tube-like pore geometry, more than one peak of translocation time distribution can be generated for proper pore diameter and applied field strengths. Both repulsive Weeks-Chandler-Anderson and attractive Lennard-Jones polymer-nanopore interaction were studied. Attraction facilitates the translocation process by shortening the total translocation time and dramatically improve the capturing of polymer chain. The width of the translocation time distribution was found to decrease with increasing temperature, increasing field strength, and decreasing pore diameter.

Strong polymer-turbulence interactions in viscoelastic turbulent channel flow.

PubMed

Dallas, V; Vassilicos, J C; Hewitt, G F

2010-12-01

This paper is focused on the fundamental mechanism(s) of viscoelastic turbulence that leads to polymer-induced turbulent drag reduction phenomenon. A great challenge in this problem is the computation of viscoelastic turbulent flows, since the understanding of polymer physics is restricted to mechanical models. An effective state-of-the-art numerical method to solve the governing equation for polymers modeled as nonlinear springs, without using any artificial assumptions as usual, was implemented here on a three-dimensional channel flow geometry. The capability of this algorithm to capture the strong polymer-turbulence dynamical interactions is depicted on the results, which are much closer qualitatively to experimental observations. This allowed a more detailed study of the polymer-turbulence interactions, which yields an enhanced picture on a mechanism resulting from the polymer-turbulence energy transfers.

Thermal-vacuum response of polymer matrix composites in space

NASA Technical Reports Server (NTRS)

Tennyson, R. C.; Matthews, R.

1993-01-01

This report describes a thermal-vacuum outgassing model and test protocol for predicting outgassing times and dimensional changes for polymer matrix composites. Experimental results derived from 'control' samples are used to provide the basis for analytical predictions to compare with the outgassing response of Long Duration Exposure Facility (LDEF) flight samples. Coefficient of thermal expansion (CTE) data are also presented. In addition, an example is given illustrating the dimensional change of a 'zero' CTE laminate due to moisture outgassing.

Interplay of non-Markov and internal friction effects in the barrier crossing kinetics of biopolymers: insights from an analytically solvable model.

PubMed

Makarov, Dmitrii E

2013-01-07

Conformational rearrangements in biomolecules (such as protein folding or enzyme-ligand binding) are often interpreted in terms of low-dimensional models of barrier crossing such as Kramers' theory. Dimensionality reduction, however, entails memory effects; as a result, the effective frictional drag force along the reaction coordinate nontrivially depends on the time scale of the transition. Moreover, when both solvent and "internal" friction effects are important, their interplay results in a highly nonlinear dependence of the effective friction on solvent viscosity that is not captured by common phenomenological models of barrier crossing. Here, these effects are illustrated using an analytically solvable toy model of an unstructured polymer chain involved in an inter- or intramolecular transition. The transition rate is calculated using the Grote-Hynes and Langer theories, which--unlike Kramers' theory--account for memory. The resulting effective frictional force exerted by the polymer along the reaction coordinate can be rationalized in terms of the effective number of monomers engaged in the transition. Faster transitions (relative to the polymer reconfiguration time scale) involve fewer monomers and, correspondingly, lower friction forces, because the polymer chain does not have enough time to reconfigure in response to the transition.

Two-dimensional Zn(II) and one-dimensional Co(II) coordination polymers based on benzene-1,4-dicarboxylate and pyridine ligands.

PubMed

Zhou, Li-Juan; Han, Chang-Bao; Wang, Yu-Ling

2016-02-01

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-dicarboxylic acid (H2BDC) and pyridine (py) with Zn(II) or Co(II) yielded two new coordination polymers, namely, poly[(μ4-benzene-1,4-dicarboxylato-κ(4)O:O':O'':O''')(pyridine-κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena-poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(3)O:O':O'')bis(pyridine-κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the Zn(II) cation is five-coordinated by four carboxylate O atoms from four BDC(2-) ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxylate groups bridge two Zn(II) ions to form centrosymmetric paddle-wheel-like Zn2(μ2-COO)4 units, which are linked by the benzene rings of the BDC(2-) ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supramolecular structure with the help of π-π stacking interactions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co2(μ2-COO)2 units. The Co(II) cations are bridged by BDC(2-) ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC(2-) ligands, one water O atom and two pyridine N atoms. Interchain O-H...O hydrogen-bonding interactions link these chains to form a three-dimensional supramolecular architecture.

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

Yan, Hao; Yang, Fan; Pan, Ding

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. Furthermore, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistrymore » through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain.« less

Simple Model of Sickle Hemoglobin

NASA Astrophysics Data System (ADS)

Shiryayev, Andrey; Li, Xiaofei; Gunton, James

2006-03-01

A microscopic model is proposed for the interactions between sickle hemoglobin molecules based on information from the protein data bank. A Monte Carlo simulation of a simplified two patch model is carried out, with the goal of understanding fiber formation. A gradual transition from monomers to one dimensional chains is observed as one varies the density of molecules at fixed temperature, somewhat similar to the transition from monomers to polymer fibers in sickle hemoglobin molecules in solution. An observed competition between chain formation and crystallization for the model is also discussed. The results of the simulation of the equation of state are shown to be in excellent agreement with a theory for a model of globular proteins, for the case of two interacting sites.

Constitutive Modeling of Nanotube/Polymer Composites with Various Nanotube Orientations

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Gates, Thomas S.

2002-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT) with various orientations with respect to the bulk material coordinates. A nanotube, the local polymer adjacent to the nanotube, and the nanotube/polymer interface have been modeled as an equivalent-continuum fiber by using an equivalent-continuum modeling method. The equivalent-continuum fiber accounts for the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composite. As an example, the proposed approach is used for the constitutive modeling of a SWNT/LaRC-SI (with a PmPV interface) composite system, with aligned nanotubes, three-dimensionally randomly oriented nanotubes, and nanotubes oriented with varying degrees of axisymmetry. It is shown that the Young s modulus is highly dependent on the SWNT orientation distribution.

Micromold methods for fabricating perforated substrates and for preparing solid polymer electrolyte composite membranes

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

Mittelsteadt, Cortney; Argun, Avni; Laicer, Castro

In polymer electrolyte membrane (PEM) fuel cells and electrolyzes, attaining and maintaining high membrane conductivity and durability is crucial for performance and efficiency. The use of low equivalent weight (EW) perfluorinated ionomers is one of the few options available to improve membrane conductivity. However, excessive dimensional changes of low EW ionomers upon application of wet/dry or freeze/thaw cycles yield catastrophic losses in membrane integrity. Incorporation of ionomers within porous, dimensionally-stable perforated polymer electrolyte membrane substrates provides improved PEM performance and longevity. The present invention provides novel methods using micromolds to fabricate the perforated polymer electrolyte membrane substrates. These novel methodsmore » using micromolds create uniform and well-defined pore structures. In addition, these novel methods using micromolds described herein may be used in batch or continuous processing.« less

Modeling Percolation in Polymer Nanocomposites by Stochastic Microstructuring

PubMed Central

Soto, Matias; Esteva, Milton; Martínez-Romero, Oscar; Baez, Jesús; Elías-Zúñiga, Alex

2015-01-01

A methodology was developed for the prediction of the electrical properties of carbon nanotube-polymer nanocomposites via Monte Carlo computational simulations. A two-dimensional microstructure that takes into account waviness, fiber length and diameter distributions is used as a representative volume element. Fiber interactions in the microstructure are identified and then modeled as an equivalent electrical circuit, assuming one-third metallic and two-thirds semiconductor nanotubes. Tunneling paths in the microstructure are also modeled as electrical resistors, and crossing fibers are accounted for by assuming a contact resistance associated with them. The equivalent resistor network is then converted into a set of linear equations using nodal voltage analysis, which is then solved by means of the Gauss–Jordan elimination method. Nodal voltages are obtained for the microstructure, from which the percolation probability, equivalent resistance and conductivity are calculated. Percolation probability curves and electrical conductivity values are compared to those found in the literature. PMID:28793594

Visualization of Au Nanoparticles Buried in a Polymer Matrix by Scanning Thermal Noise Microscopy

PubMed Central

Yao, Atsushi; Kobayashi, Kei; Nosaka, Shunta; Kimura, Kuniko; Yamada, Hirofumi

2017-01-01

Several researchers have recently demonstrated visualization of subsurface features with a nanometer-scale resolution using various imaging schemes based on atomic force microscopy. Since all these subsurface imaging techniques require excitation of the oscillation of the cantilever and/or sample surface, it has been difficult to identify a key imaging mechanism. Here we demonstrate visualization of Au nanoparticles buried 300 nm into a polymer matrix by measurement of the thermal noise spectrum of a microcantilever with a tip in contact to the polymer surface. We show that the subsurface Au nanoparticles are detected as the variation in the contact stiffness and damping reflecting the viscoelastic properties of the polymer surface. The variation in the contact stiffness well agrees with the effective stiffness of a simple one-dimensional model, which is consistent with the fact that the maximum depth range of the technique is far beyond the extent of the contact stress field. PMID:28210001

Theory of Random Copolymer Fractionation in Columns

NASA Astrophysics Data System (ADS)

Enders, Sabine

Random copolymers show polydispersity both with respect to molecular weight and with respect to chemical composition, where the physical and chemical properties depend on both polydispersities. For special applications, the two-dimensional distribution function must adjusted to the application purpose. The adjustment can be achieved by polymer fractionation. From the thermodynamic point of view, the distribution function can be adjusted by the successive establishment of liquid-liquid equilibria (LLE) for suitable solutions of the polymer to be fractionated. The fractionation column is divided into theoretical stages. Assuming an LLE on each theoretical stage, the polymer fractionation can be modeled using phase equilibrium thermodynamics. As examples, simulations of stepwise fractionation in one direction, cross-fractionation in two directions, and two different column fractionations (Baker-Williams fractionation and continuous polymer fractionation) have been investigated. The simulation delivers the distribution according the molecular weight and chemical composition in every obtained fraction, depending on the operative properties, and is able to optimize the fractionation effectively.

Field-scale simulation of chemical flooding

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

Saad, N.

1989-01-01

A three-dimensional compositional chemical flooding simulator (UTCHEM) has been improved. The new mathematical formulation, boundary conditions, and a description of the physicochemical models of the simulator are presented. This improved simulator has been used for the study of the low tension pilot project at the Big Muddy field near Casper, Wyoming. Both the tracer injection conducted prior to the injection of the chemical slug, and the chemical flooding stages of the pilot project, have been analyzed. Not only the oil recovery but also the tracers, polymer, alcohol and chloride histories have been successfully matched with field results. Simulation results indicatemore » that, for this fresh water reservoir, the salinity gradient during the preflush and the resulting calcium pickup by the surfactant slug played a major role in the success of the project. In addition, analysis of the effects of the crossflow on the performance of the pilot project indicates that, for the well spacing of the pilot, crossflow does not play as important a role as it might for a large-scale project. To improve the numerical efficiency of the simulator, a third order convective differencing scheme has been applied to the simulator. This method can be used with non-uniform mesh, and therefore is suited for simulation studies of large-scale multiwell heterogeneous reservoirs. Comparison of the results with one and two dimensional analytical solutions shows that this method is effective in eliminating numerical dispersion using relatively large grid blocks. Results of one, two and three-dimensional miscible water/tracer flow, water flooding, polymer flooding, and micellar-polymer flooding test problems, and results of grid orientation studies, are presented.« less

Development of an alkaline/surfactant/polymer compositional reservoir simulator

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

Bhuyan, D.

1989-01-01

The mathematical formulation of a generalized three-dimensional compositional reservoir simulator for high-pH chemical flooding processes is presented in this work. The model assumes local thermodynamic equilibrium with respect to both reaction chemistry and phase behavior and calculates equilibrium electrolyte and phase compositions as a function of time and position. The reaction chemistry considers aqueous electrolytic chemistry, precipitation/dissolution of minerals, ion exchange reactions on matrix surface, reaction of acidic components of crude oil with the bases in the aqueous solution and cation exchange reactions with the micelles. The simulator combines this detailed reaction chemistry associated with these processes with the extensivemore » physical and flow property modeling schemes of an existing chemical flood simulator (UTCHEM) to model the multiphase, multidimensional displacement processes. The formulation of the chemical equilibrium model is quite general and is adaptable to simulate a variety of chemical descriptions. In addition to its use in the simulation of high-pH chemical flooding processes, the model will find application in the simulation of other reactive flow problems like the ground water contamination, reinjection of produced water, chemical waste disposal, etc. in one, two or three dimensions and under multiphase flow conditions. In this work, the model is used to simulate several hypothetical cases of high-pH chemical floods, which include cases from a simple alkaline preflush of a micellar/polymer flood to surfactant enhanced alkaline-polymer flooding and the results are analyzed. Finally, a few published alkaline, alkaline-polymer and surfactant-alkaline-polymer corefloods are simulated and compared with the experimental results.« less

Mathematical Modeling and Optimization Studies on Development of Fuel Cells for Multifarious Applications

DTIC Science & Technology

2010-05-12

multicomponent steady-state model for liquid -feed solid polymer electrolyte DBFCs. These fuel cells use sodium borohydride (NaBH4) in alkaline media...layers, diffusion layers and the polymer electrolyte membrane for a liquid feed DBFC. Diffusion of reactants within and between the pores is accounted...projected for futuristic portable applications. In this project we developed a three- dimensional, multicomponent steady-state model for liquid -feed solid

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide.

PubMed

Wen, Li-Li; Dang, Dong-Bin; Duan, Chun-Ying; Li, Yi-Zhi; Tian, Zheng-Fang; Meng, Qing-Jin

2005-10-03

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.

Polymer model with Epigenetic Recoloring Reveals a Pathway for the de novo Establishment and 3D Organization of Chromatin Domains

NASA Astrophysics Data System (ADS)

Michieletto, D.; Orlandini, E.; Marenduzzo, D.

2016-10-01

One of the most important problems in development is how epigenetic domains can first be established, and then maintained, within cells. To address this question, we propose a framework that couples three-dimensional chromatin folding dynamics to a "recoloring" process modeling the writing of epigenetic marks. Because many intrachromatin interactions are mediated by bridging proteins, we consider a "two-state" model with self-attractive interactions between two epigenetic marks that are alike (either active or inactive). This model displays a first-order-like transition between a swollen, epigenetically disordered phase and a compact, epigenetically coherent chromatin globule. If the self-attraction strength exceeds a threshold, the chromatin dynamics becomes glassy, and the corresponding interaction network freezes. By modifying the epigenetic read-write process according to more biologically inspired assumptions, our polymer model with recoloring recapitulates the ultrasensitive response of epigenetic switches to perturbations and accounts for long-lived multidomain conformations, strikingly similar to the topologically associating domains observed in eukaryotic chromosomes.

Fully Resolved Simulations of 3D Printing

NASA Astrophysics Data System (ADS)

Tryggvason, Gretar; Xia, Huanxiong; Lu, Jiacai

2017-11-01

Numerical simulations of Fused Deposition Modeling (FDM) (or Fused Filament Fabrication) where a filament of hot, viscous polymer is deposited to ``print'' a three-dimensional object, layer by layer, are presented. A finite volume/front tracking method is used to follow the injection, cooling, solidification and shrinking of the filament. The injection of the hot melt is modeled using a volume source, combined with a nozzle, modeled as an immersed boundary, that follows a prescribed trajectory. The viscosity of the melt depends on the temperature and the shear rate and the polymer becomes immobile as its viscosity increases. As the polymer solidifies, the stress is found by assuming a hyperelastic constitutive equation. The method is described and its accuracy and convergence properties are tested by grid refinement studies for a simple setup involving two short filaments, one on top of the other. The effect of the various injection parameters, such as nozzle velocity and injection velocity are briefly examined and the applicability of the approach to simulate the construction of simple multilayer objects is shown. The role of fully resolved simulations for additive manufacturing and their use for novel processes and as the ``ground truth'' for reduced order models is discussed.

A three-dimensional transient mixed hybrid finite element model for superabsorbent polymers with strain-dependent permeability.

PubMed

Yu, Cong; Malakpoor, Kamyar; Huyghe, Jacques M

2018-05-16

A hydrogel is a cross-linked polymer network with water as solvent. Industrially widely used superabsorbent polymers (SAP) are partially neutralized sodium polyacrylate hydrogels. The extremely large degree of swelling is one of the most distinctive characteristics of such hydrogels, as the volume increase can be about 30 times its original volume when exposed to physiological solution. The large deformation resulting from the swelling demands careful numerical treatment. In this work, we present a biphasic continuum-level swelling model using the mixed hybrid finite element method (MHFEM) in three dimensions. The hydraulic permeability is highly dependent on the swelling ratio, resulting in values that are orders of magnitude apart from each other. The property of the local mass conservation of MHFEM contributes to a more accurate calculation of the deformation as the permeability across the swelling gel in a transient state is highly non-uniform. We show that the proposed model is able to simulate the free swelling of a random-shaped gel and the squeezing of fluid out of a swollen gel. Finally, we make use of the proposed numerical model to study the onset of surface instability in transient swelling.

Dynamics of Polarons in Organic Conjugated Polymers with Side Radicals.

PubMed

Liu, J J; Wei, Z J; Zhang, Y L; Meng, Y; Di, B

2017-03-16

Based on the one-dimensional tight-binding Su-Schrieffer-Heeger (SSH) model, and using the molecular dynamics method, we discuss the dynamics of electron and hole polarons propagating along a polymer chain, as a function of the distance between side radicals and the magnitude of the transfer integrals between the main chain and the side radicals. We first discuss the average velocities of electron and hole polarons as a function of the distance between side radicals. It is found that the average velocities of the electron polarons remain almost unchanged, while the average velocities of hole polarons decrease significantly when the radical distance is comparable to the polaron width. Second, we have found that the average velocities of electron polarons decrease with increasing transfer integral, but the average velocities of hole polarons increase. These results may provide a theoretical basis for understanding carriers transport properties in polymers chain with side radicals.

DNA molecules on periodically microstructured lipid membranes: Localization and coil stretching

NASA Astrophysics Data System (ADS)

Hochrein, Marion B.; Leierseder, Judith A.; Golubović, Leonardo; Rädler, Joachim O.

2007-02-01

We explore large scale conformations of DNA molecules adsorbed on curved surfaces. For that purpose, we investigate the behavior of DNA adsorbed on periodically shaped cationic lipid membranes. These unique membrane morphologies are supported on grooved, one-dimensionally periodic microstructured surfaces. Strikingly, we find that these periodically structured membranes are capable to stretch DNA coils. We elucidate this phenomenon in terms of surface curvature dependent potential energy attained by the adsorbed DNA molecules. Due to it, DNA molecules undergo a localization transition causing them to stretch by binding to highly curved sections (edges) of the supported membranes. This effect provides a new venue for controlling conformations of semiflexible polymers such as DNA by employing their interactions with specially designed biocompatible surfaces. We report the first experimental observation of semiflexible polymers unbinding transition in which DNA molecules unbind from one-dimensional manifolds (edges) while remaining bound to two-dimensional manifolds (cationic membranes).

Topical Review: Polymer gel dosimetry

PubMed Central

Baldock, C; De Deene, Y; Doran, S; Ibbott, G; Jirasek, A; Lepage, M; McAuley, K B; Oldham, M; Schreiner, L J

2010-01-01

Polymer gel dosimeters are fabricated from radiation sensitive chemicals which, upon irradiation, polymerize as a function of the absorbed radiation dose. These gel dosimeters, with the capacity to uniquely record the radiation dose distribution in three-dimensions (3D), have specific advantages when compared to one-dimensional dosimeters, such as ion chambers, and two-dimensional dosimeters, such as film. These advantages are particularly significant in dosimetry situations where steep dose gradients exist such as in intensity-modulated radiation therapy (IMRT) and stereotactic radiosurgery. Polymer gel dosimeters also have specific advantages for brachytherapy dosimetry. Potential dosimetry applications include those for low-energy x-rays, high-linear energy transfer (LET) and proton therapy, radionuclide and boron capture neutron therapy dosimetries. These 3D dosimeters are radiologically soft-tissue equivalent with properties that may be modified depending on the application. The 3D radiation dose distribution in polymer gel dosimeters may be imaged using magnetic resonance imaging (MRI), optical-computerized tomography (optical-CT), x-ray CT or ultrasound. The fundamental science underpinning polymer gel dosimetry is reviewed along with the various evaluation techniques. Clinical dosimetry applications of polymer gel dosimetry are also presented. PMID:20150687

Detection of Macromolecular Fractions in HCN Polymers Using Electrophoretic and Ultrafiltration Techniques.

PubMed

Marín-Yaseli, Margarita R; Cid, Cristina; Yagüe, Ana I; Ruiz-Bermejo, Marta

2017-02-01

Elucidating the origin of life involves synthetic as well as analytical challenges. Herein, for the first time, we describe the use of gel electrophoresis and ultrafiltration to fractionate HCN polymers. Since the first prebiotic synthesis of adenine by Oró, HCN polymers have gained much interest in studies on the origins of life due to the identification of biomonomers and related compounds within them. Here, we demonstrate that macromolecular fractions with electrophoretic mobility can also be detected within HCN polymers. The migration of polymers under the influence of an electric field depends not only on their sizes (one-dimensional electrophoresis) but also their different isoelectric points (two-dimensional electrophoresis, 2-DE). The same behaviour was observed for several macromolecular fractions detected in HCN polymers. Macromolecular fractions with apparent molecular weights as high as 250 kDa were detected by tricine-SDS gel electrophoresis. Cationic macromolecular fractions with apparent molecular weights as high as 140 kDa were also detected by 2-DE. The HCN polymers synthesized were fractionated by ultrafiltration. As a result, the molecular weight distributions of the macromolecular fractions detected in the HCN polymers directly depended on the synthetic conditions used to produce these polymers. The implications of these results for prebiotic chemistry will be discussed. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

The numerical study of the coextrusion process of polymer melts in the cable head

NASA Astrophysics Data System (ADS)

Kozitsyna, M. V.; Trufanova, N. M.

2017-06-01

The process of coextrusion consists in a simultaneous creation of all necessary insulating layers of different polymers in the channel of a special forming tool. The main focus of this study is the analysis of technological, geometrical and rheological characteristics on the values of the layer’s thickness. In this paper are considered three geometries of cable head on the three-dimensional and two-dimensional representation. The mathematical models of separate and joint flow of polymer melts have been implemented by the finite element method in Ansys software package. The velocity fields, temperature, pressure in the cross-sections of the channel and by the length have been obtained. The influence of some thickness characteristics of insulation layers has been identified.

3-Dimensional Computational Fluid Dynamics Modeling of Solid Oxide Fuel Cell Using Different Fuels

DTIC Science & Technology

2011-01-01

major types of fuel cells in practice are listed below: Polymer Electrolyte Membrane Fuel Cell ( PEMFC ) Alkaline Fuel cell (AFC) Phosphoric Acid...Material Operating Temperature (oC) Efficiency (%) PEMFC H2, Methanol, Formic Acid Hydrated Organic Polymer < 90 40-50 AFC Pure H2 Aqueous

Drag reduction in the turbulent Kolmogorov flow.

PubMed

Boffetta, Guido; Celani, Antonio; Mazzino, Andrea

2005-03-01

We investigate the phenomenon of drag reduction in a viscoelastic fluid model of dilute polymer solutions. By means of direct numerical simulations of the three-dimensional turbulent Kolmogorov flow we show that drag reduction takes place above a critical Reynolds number Re(c). An explicit expression for the dependence of Re(c) on polymer elasticity and diffusivity is derived. The values of the drag coefficient obtained for different fluid parameters collapse onto a universal curve when plotted as a function of the rescaled Reynolds number Re/ Re(c). The analysis of the momentum budget allows us to gain some insight on the physics of drag reduction, and suggests the existence of a Re-independent value of the drag cofficient--lower than the Newtonian one--for large Reynolds numbers.

Sterically controlled mechanochemistry under hydrostatic pressure

DOE PAGES

Yan, Hao; Yang, Fan; Pan, Ding; ...

2018-02-21

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. Furthermore, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistrymore » through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain.« less

Micro sculpting technology using DPSSL

NASA Astrophysics Data System (ADS)

Chang, Won-Seok; Shin, Bosung; Kim, Jae-gu; Whang, Kyung-Hyun

2003-11-01

Multiple pulse laser ablation of polymer is performed with DPSS (Diode Pumped Solid State) 3rd harmonic Nd:YVO4 laser (355 nm) in order to fabricate three-dimensional micro components. Here we considered mechanistic aspects of the interaction between UV laser and polymer to obtain optimum process conditions for maskless photomachining using DPSSL. The photo-physical and photochemical parameters such as laser wavelength and optical characteristics of polymers are investigated by experiments to reduce plume effect, which induce the re-deposited debris on the surface of substrate. In this study, LDST (laser direct sculpting technique) are developed to gain various three-dimensional shape with size less than 500 micrometer. Main process sequences are from rapid prototyping technology such as CAD/CAM modeling of products, machining path generation, layer-by-layer machining, and so on. This method can be applied to manufacture the prototype of micro device and the polymer mould for mass production without expensive mask fabrication.

Controlled Interactions between Two Dimensional Layered Inorganic Nanosheets and Polymers

DTIC Science & Technology

2016-06-15

with end-functionalized polymers . First, an end-functionalized polymer with conjugated end-molecule, pyrene, is successfully employed to boron... polymers . First, an end-functionalized polymer with conjugated end-molecule, pyrenes, is successfully employed to boron nitride nanosheets (BNNS), and...AFRL-AFOSR-JP-TR-2016-0071 Controlled Interactions between Two Dimensional Layered Inorganic Nanosheets and Polymers Cheolmin Park YONSEI UNIVERSITY

Two-dimensional electron beam charging model for polymer films

NASA Technical Reports Server (NTRS)

Reeves, R. D.; Balmain, K. G.

1981-01-01

A two-dimensional model is developed to describe the charging of strips of thin polymer films above a grounded substrate exposed to a uniform mono-energetic electron beam. The study is motivated by the observed anomalous behavior of geosynchronous satellites, which has been attributed to differential charging of the satellite surfaces exposed to magnetospheric electrons. Surface and bulk electric fields are calcuated at steady state in order to identify regions of high electrical stress, with emphasis on behavior near the material's edge. The model is used to study the effects of some of the experimental parameters, notably beam energy, beam angle of incidence, beam current density, material thickness and material width. Also examined are the consequences of a central gap in the material and a discontinuity in the material thickness.

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.

Chromatic control in coextruded layered polymer microlenses

NASA Astrophysics Data System (ADS)

Crescimanno, Michael; Oder, Tom N.; Andrews, James H.; Zhou, Chuanhong; Petrus, Joshua B.; Merlo, Cory; Bagheri, Cameron; Hetzel, Connor; Tancabel, James; Singer, Kenneth D.; Baer, Eric

2014-12-01

We describe the formation, characterization and theoretical understanding of microlenses comprised of alternating polystyrene and polymethylmethacrylate layers produced by multilayer coextrusion. These lenses are fabricated by photolithography, using a grayscale mask followed by plasma etching, so that the refractive index alternation of the bilayer stack appears across the radius of the microlens. The alternating quarter-wave thick layers form a one-dimensional photonic crystal whose dispersion augments the material dispersion, allowing one to sculpt the chromatic dispersion of the lens by adjusting the layered structure. Using Huygen's principle, we model our experimental measurements of the focal length of these lenses across the reflection band of the multilayer polymer film from which the microlens is fashioned. For a 56 micron diameter multilayered lens of focal length 300 microns, we measured a nearly 25 percent variation in the focal length across a shallow, 50 nm-wide reflection band.

High Strain Rate Deformation Modeling of a Polymer Matrix Composite. Part 2; Composite Micromechanical Model

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.; Stouffer, Donald C.

1998-01-01

Recently applications have exposed polymer matrix composite materials to very high strain rate loading conditions, requiring an ability to understand and predict the material behavior under these extreme conditions. In this second paper of a two part report, a three-dimensional composite micromechanical model is described which allows for the analysis of the rate dependent, nonlinear deformation response of a polymer matrix composite. Strain rate dependent inelastic constitutive equations utilized to model the deformation response of a polymer are implemented within the micromechanics method. The deformation response of two representative laminated carbon fiber reinforced composite materials with varying fiber orientation has been predicted using the described technique. The predicted results compare favorably to both experimental values and the response predicted by the Generalized Method of Cells, a well-established micromechanics analysis method.

Free-standing membrane polymer laser on the end of an optical fiber

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

Zhai, Tianrui, E-mail: trzhai@bjut.edu.cn, E-mail: zhangxinping@bjut.edu.cn; Li, Songtao; Hu, Yujie

2016-01-25

One- and two-dimensional distributed feedback cavities were constructed on free-standing polymer membranes using spin-coating and lift-off techniques. Low threshold lasing was generated through feedback amplification when the 290-nm membrane device was optically pumped, which was attributed to the strong confinement mechanism provided by the active waveguide layer without a substrate. The free-standing membrane polymer laser is flexible and can be transplanted. Single- and dual-wavelength fiber lasers were achieved by directly attaching the membrane polymer laser on the optical fiber end face. This technique provides potential to fabricate polymer lasers on surfaces with arbitrary shapes.

Functional Supramolecular Polymers*

PubMed Central

Aida, T.; Meijer, E.W.; Stupp, S.I.

2012-01-01

Supramolecular polymers can be random and entangled coils with the mechanical properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramolecular polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among molecular subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramolecular assemblies of the cell cytoskeleton, and possess useful biological and electronic functions. PMID:22344437

Low-dimensional manifold of actin polymerization dynamics

NASA Astrophysics Data System (ADS)

Floyd, Carlos; Jarzynski, Christopher; Papoian, Garegin

2017-12-01

Actin filaments are critical components of the eukaryotic cytoskeleton, playing important roles in a number of cellular functions, such as cell migration, organelle transport, and mechanosensation. They are helical polymers with a well-defined polarity, composed of globular subunits that bind nucleotides in one of three hydrolysis states (ATP, ADP-Pi, or ADP). Mean-field models of the dynamics of actin polymerization have succeeded in, among other things, determining the nucleotide profile of an average filament and resolving the mechanisms of accessory proteins. However, these models require numerical solution of a high-dimensional system of nonlinear ordinary differential equations. By truncating a set of recursion equations, the Brooks-Carlsson (BC) model reduces dimensionality to 11, but it still remains nonlinear and does not admit an analytical solution, hence, significantly hindering understanding of its resulting dynamics. In this work, by taking advantage of the fast timescales of the hydrolysis states of the filament tips, we propose two model reduction schemes: the quasi steady-state approximation model is five-dimensional and nonlinear, whereas the constant tip (CT) model is five-dimensional and linear, resulting from the approximation that the tip states are not dynamic variables. We provide an exact solution of the CT model and use it to shed light on the dynamical behaviors of the full BC model, highlighting the relative ordering of the timescales of various collective processes, and explaining some unusual dependence of the steady-state behavior on initial conditions.

Design and Fabrication of a Large-Stroke Deformable Mirror Using a Gear-Shape Ionic-Conductive Polymer Metal Composite

PubMed Central

Wei, Hsiang-Chun; Su, Guo-Dung John

2012-01-01

Conventional camera modules with image sensors manipulate the focus or zoom by moving lenses. Although motors, such as voice-coil motors, can move the lens sets precisely, large volume, high power consumption, and long moving time are critical issues for motor-type camera modules. A deformable mirror (DM) provides a good opportunity to improve these issues. The DM is a reflective type optical component which can alter the optical power to focus the lights on the two dimensional optical image sensors. It can make the camera system operate rapidly. Ionic polymer metal composite (IPMC) is a promising electro-actuated polymer material that can be used in micromachining devices because of its large deformation with low actuation voltage. We developed a convenient simulation model based on Young's modulus and Poisson's ratio. We divided an ion exchange polymer, also known as Nafion®, into two virtual layers in the simulation model: one was expansive and the other was contractive, caused by opposite constant surface forces on each surface of the elements. Therefore, the deformation for different IPMC shapes can be described more easily. A standard experiment of voltage vs. tip displacement was used to verify the proposed modeling. Finally, a gear shaped IPMC actuator was designed and tested. Optical power of the IPMC deformable mirror is experimentally demonstrated to be 17 diopters with two volts. The needed voltage was about two orders lower than conventional silicon deformable mirrors and about one order lower than the liquid lens. PMID:23112648

Characterization and modeling of viscoelastic behavior of carbon nanotube reinforced polymers: The influence of interphase and nanotube morphology

NASA Astrophysics Data System (ADS)

Liu, Hua

The addition of nanoparticles into polymer materials has been observed to dramatically change the mechanical, thermal, electrical, and diffusion properties of the host polymers, promising a novel class of polymer matrix composite materials with superior properties and added functionalities that are ideal candidates in many applications, including aerospace, automobile, medical devices, and sporting goods. Understanding the behavior and underlying mechanisms of these polymer nanocomposites is critical. The research work presented in this dissertation represents one of the initial efforts in the long journey pursuing the ultimate understanding of nanoparticle reinforced polymer systems. Particular focal points are experimental evaluation and the development of appropriate modeling methods to capture the influence of the interphase on the overall viscoelastic behavior of carbon nanotube reinforced polymer nanocomposites. The first portion of this dissertation study investigates the viscoelastic behavior of MWCNT based PMMA nanocomposites, which complements our previous study of SWCNT/PMMA systems to confirm functionalization of nanotubes as an effective way to manipulate the interaction between nanotube and polymers and control the properties of the interphase region forming around the nanotubes and consequently change the overall performance of nanotube based polymer nanocomposites. In the second portion of this dissertation, we present a novel hybrid numerical-analytical modeling method that is capable of predicting viscoelastic behavior of multiphase polymer nanocomposites, in which the nanoscopic fillers can assume complex configurations. By combining the finite element technique and a micromechanical approach (particularly, the Mori-Tanaka method) with local phase properties, this method operates at low computational cost and effectively accounts for the influence of the interphase as well as in situ nanoparticle morphology. This modeling method is implemented two-dimensionally on nanotube and nanoplatelet based polymer nanocomposites. Given the experimentally measured frequency domain response of the bulk polymer, the viscoelastic behavior of the nanocomposites in both frequency and temperature domains can be calculated. The predicted pattern of influence of the interphase on the overall performance of the nanocomposites is consistent with the experimental observation. 3D parametric studies utilizing this modeling technique reveal that the nanotube morphology "modifies" the effect of interphase and hence profoundly influences the overall viscoelastic behavior. The findings help explain some experimental observations and furthermore, draw attention to the importance of morphology control through appropriate synthesis and processing techniques to further tune the thermomechanical behavior of the nanocomposites.

Transition records of stationary Markov chains.

PubMed

Naudts, Jan; Van der Straeten, Erik

2006-10-01

In any Markov chain with finite state space the distribution of transition records always belongs to the exponential family. This observation is used to prove a fluctuation theorem, and to show that the dynamical entropy of a stationary Markov chain is linear in the number of steps. Three applications are discussed. A known result about entropy production is reproduced. A thermodynamic relation is derived for equilibrium systems with Metropolis dynamics. Finally, a link is made with recent results concerning a one-dimensional polymer model.

Distribution of dopant ions around poly(3,4-ethylenedioxythiophene) chains: a theoretical study.

PubMed

Casanovas, Jordi; Zanuy, David; Alemán, Carlos

2017-04-12

The effect of counterions and multiple polymer chains on the properties and structure of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with ClO 4 - has been examined using density functional theory (DFT) calculations with periodic boundary conditions (PBCs). Calculations on a one-dimensional periodic model with four explicit polymer repeat units and two ClO 4 - molecules indicate that the latter are separated as much as possible, with the salt structure and band gap obtained from such ClO 4 - distribution being in excellent agreement with those determined experimentally. On the other hand, DFT calculations on periodic models that include two chains indicate that neighboring PEDOT chains are shifted along the molecular axis by a half of the repeat unit length, with dopant ions intercalated between the polymer molecules acting as cement. In order to support these structural features, classical molecular dynamics (MD) simulations have been performed on a multiphasic system consisting of 69 explicit PEDOT chains anchored onto a steel surface, explicit ClO 4 - anions embedded in the polymer matrix, and an acetonitrile phase layer onto the polymer matrix. Analyses of the radial distribution functions indicate that the all-anti conformation, the relative disposition of adjacent PEDOT chains and the distribution of ClO 4 - dopant ions are fully consistent with periodic DFT predictions. The agreement between two such different methodologies allows reinforcing the microscopic understanding of the PEDOT film structure.

Adsorption of poly(ethylene succinate) chain onto graphene nanosheets: A molecular simulation.

PubMed

Kelich, Payam; Asadinezhad, Ahmad

2016-09-01

Understanding the interaction between single polymer chain and graphene nanosheets at local and global length scales is essential for it underlies the mesoscopic properties of polymer nanocomposites. A computational attempt was then performed using atomistic molecular dynamics simulation to gain physical insights into behavior of a model aliphatic polyester, poly(ethylene succinate), single chain near graphene nanosheets, where the effects of the polymer chain length, graphene functionalization, and temperature on conformational properties of the polymer were studied comparatively. Graphene functionalization was carried out through extending the parameters set of an all-atom force field. The results showed a significant conformational transition of the polymer chain from three-dimensional statistical coil, in initial state, to two-dimensional fold, in final state, during adsorption on graphene. The conformational order, overall shape, end-to-end separation statistics, and mobility of the polymer chain were found to be influenced by the graphene functionalization, temperature, and polymer chain length. Furthermore, the polymer chain dynamics mode during adsorption on graphene was observed to transit from normal diffusive to slow subdiffusive mode. The findings from this computational study could shed light on the physics of the early stages of aliphatic polyester chain organization induced by graphene. Copyright © 2016 Elsevier Inc. All rights reserved.

Self-consistent field theory of tethered polymers: one dimensional, three dimensional, strong stretching theories and the effects of excluded-volume-only interactions.

PubMed

Suo, Tongchuan; Whitmore, Mark D

2014-11-28

We examine end-tethered polymers in good solvents, using one- and three-dimensional self-consistent field theory, and strong stretching theories. We also discuss different tethering scenarios, namely, mobile tethers, fixed but random ones, and fixed but ordered ones, and the effects and important limitations of including only binary interactions (excluded volume terms). We find that there is a "mushroom" regime in which the layer thickness is independent of the tethering density, σ, for systems with ordered tethers, but we argue that there is no such plateau for mobile or disordered anchors, nor is there one in the 1D theory. In the other limit of brushes, all approaches predict that the layer thickness scales linearly with N. However, the σ(1/3) scaling is a result of keeping only excluded volume interactions: when the full potential is included, the dependence is faster and more complicated than σ(1/3). In fact, there does not appear to be any regime in which the layer thickness scales in the combination Nσ(1/3). We also compare the results for two different solvents with each other, and with earlier Θ solvent results.

Ameba-like diffusion in two-dimensional polymer melts: how critical exponents determine the structural relaxation

NASA Astrophysics Data System (ADS)

Kreer, Torsten; Meyer, Hendrik; Baschnagel, Joerg

2008-03-01

By means of numerical investigations we demonstrate that the structural relaxation of linear polymers in two dimensional (space-filling) melts is characterized by ameba-like diffusion, where the chains relax via frictional dissipation at their interfacial contact lines. The perimeter length of the contact line determines a new length scale, which does not exist in three dimensions. We show how this length scale follows from the critical exponents, which hence characterize not only the static but also the dynamic properties of the melt. Our data is in agreement with recent theoretical predictions, concerning the time-dependence of single-monomer mean-square displacements and the scaling of concomitant relaxation times with the degree of polymerization. For the latter we demonstrate a density crossover-scaling as an additional test for ameba-like relaxation. We compare our results to the conceptually different Rouse model, which predicts numerically close exponents. Our data can clearly rule out the classical picture as the relevant relaxation mechanism in two-dimensional polymer melts.

Research of spin-orbit interaction in organic conjugated polymers

NASA Astrophysics Data System (ADS)

Li, H.; Zhou, M. Y.; Wu, S. Y.; Liang, X. R.

2017-06-01

The effect of spin-orbit interaction on the one-dimensional organic polymer was investigated theoretically. Spin-orbital interaction led to the spatial separation of energy band but did not eliminate spin degeneration, which was different from energy level splitting in the Zeeman Effect. Spin-orbit interaction had little effect on the energy band structure, charge density, and lattice position, etc.; Spin precession was obtained when a polaron was transported along the polymer chain, which theoretically proved that it was feasible to control the spin precession of polaron in organic polymers by the use of external electric field.

Measurement and Modeling of the Ability of Crack Fillers to Prevent Chloride Ingress into Mortar.

PubMed

Jones, Scott Z; Bentz, Dale P; Davis, Jeffrey M; Hussey, Daniel S; Jacobson, David L; Molloy, John L; Sieber, John R

2017-09-01

A common repair procedures applied to damaged concrete is to fill cracks with an organic polymer. This operation is performed to increase the service life of the concrete by removing a preferential pathway for the ingress of water, chlorides, and other deleterious species. To effectively fulfill its mission of preventing chloride ingress, the polymer must not only fully fill the macro-crack, but must also intrude the damage zone surrounding the crack perimeter. Here, the performance of two commonly employed crack fillers, one epoxy, and one methacrylate, are investigated using a combined experimental and computer modeling approach. Neutron tomography and microbeam X-ray fluorescence spectrometry (μXRF) measurements are employed on pre-cracked and chloride-exposed specimens to quantify the crack filling and chloride ingress limiting abilities, respectively, of the two polymers. A two-dimensional model of chloride transport is derived from a mass balance and solved by the finite element method. Crack images provided by μXRF are used to generate the input microstructure for the simulations. When chloride binding and a time-dependent mortar diffusivity are both included in the computer model, good agreement with the experimental results is obtained. Both crack fillers significantly reduce chloride ingress during the 21 d period of the present experiments; however, the epoxy itself contains approximately 4 % by mass chlorine. Leaching studies were performed assess the epoxy as a source of deleterious ions for initiating corrosion of the steel reinforcement in concrete structures.

Synthesis, structural characterization and antitumor activity of a Ca(II) coordination polymer based on 4-formyl-1,3-benzenedisulfonate-2-furoic acid hydrazide ligands

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

Tai, Xi-Shi, E-mail: taixs@wfu.edu.cn; Wang, Xin

2017-03-15

A new Ca(II) coordination polymer, ([CaL(H{sub 2}O){sub 4}] · (H{sub 2}O){sub 4}){sub n} (L = 4-formyl-1,3-benzenedisulfonate-2-furoic acid hydrazide) has been prepared by one-pot synthesis method. And it was characterized by elemental analysis, IR and thermal analysis. The result of X-ray single-crystal diffraction analysis shows that the Ca(II) complex molecules form one-dimensional chain structure by the bridging oxygen atoms. The anti-tumor activity of L ligand and the Ca(II) coordination polymer has also been studied.

Effects of polarons on static polarizabilities and second order hyperpolarizabilities of conjugated polymers

NASA Astrophysics Data System (ADS)

Wang, Ya-Dong; Meng, Yan; Di, Bing; Wang, Shu-Ling; An, Zhong

2010-12-01

According to the one-dimensional tight-binding Su—Schrieffer—Heeger model, we have investigated the effects of charged polarons on the static polarizability, αxx, and the second order hyperpolarizabilities, γxxxx, of conjugated polymers. Our results are consistent qualitatively with previous ab initio and semi-empirical calculations. The origin of the universal growth is discussed using a local-view formalism that is based on the local atomic charge derivatives. Furthermore, combining the Su-Schrieffer-Heeger model and the extended Hubbard model, we have investigated systematically the effects of electron-electron interactions on αxx and γxxxx of charged polymer chains. For a fixed value of the nearest-neighbour interaction V, the values of αxx and γxxxx increase as the on-site Coulomb interaction U increases for U < Uc and decrease with U for U > Uc, where Uc is a critical value of U at which the static polarizability or the second order hyperpolarizability reaches a maximal value of αmax or γmax. It is found that the effect of the e-e interaction on the value of αxx is dependent on the ratio between U and V for either a short or a long charged polymer. Whereas, that effect on the value of γxxxx is sensitive both to the ratio of U to V and to the size of the molecule.

NANEX: Process design and optimization.

PubMed

Baumgartner, Ramona; Matić, Josip; Schrank, Simone; Laske, Stephan; Khinast, Johannes; Roblegg, Eva

2016-06-15

Previously, we introduced a one-step nano-extrusion (NANEX) process for transferring aqueous nano-suspensions into solid formulations directly in the liquid phase. Nano-suspensions were fed into molten polymers via a side-feeding device and excess water was eliminated via devolatilization. However, the drug content in nano-suspensions is restricted to 30 % (w/w), and obtaining sufficiently high drug loadings in the final formulation requires the processing of high water amounts and thus a fundamental process understanding. To this end, we investigated four polymers with different physicochemical characteristics (Kollidon(®) VA64, Eudragit(®) E PO, HPMCAS and PEG 20000) in terms of their maximum water uptake/removal capacity. Process parameters as throughput and screw speed were adapted and their effect on the mean residence time and filling degree was studied. Additionally, one-dimensional discretization modeling was performed to examine the complex interactions between the screw geometry and the process parameters during water addition/removal. It was established that polymers with a certain water miscibility/solubility can be manufactured via NANEX. Long residence times of the molten polymer in the extruder and low filling degrees in the degassing zone favored the addition/removal of significant amounts of water. The residual moisture content in the final extrudates was comparable to that of extrudates manufactured without water. Copyright © 2016 Elsevier B.V. All rights reserved.

Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

DOEpatents

Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

2015-02-24

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

Critical behavior of two-dimensional vesicles in the deflated regime

NASA Technical Reports Server (NTRS)

Banavar, Jayanth R.; Maritan, Amos; Stella, Attilio

1991-01-01

The critical behavior of two-dimensional vesicles in the deflated regime is studied analytically using a mapping onto a gauge model, scaling arguments, and exact inequalities. In agreement with the results of earlier studies the critical behavior is governed by a branched-polymer fixed point. The shape of the critical line in the gauge model is deduced in the weak and in the infinitely deflated regime.

Characterizing and modeling the free recovery and constrained recovery behavior of a polyurethane shape memory polymer

NASA Astrophysics Data System (ADS)

Volk, Brent L.; Lagoudas, Dimitris C.; Maitland, Duncan J.

2011-09-01

In this work, tensile tests and one-dimensional constitutive modeling were performed on a high recovery force polyurethane shape memory polymer that is being considered for biomedical applications. The tensile tests investigated the free recovery (zero load) response as well as the constrained displacement recovery (stress recovery) response at extension values up to 25%, and two consecutive cycles were performed during each test. The material was observed to recover 100% of the applied deformation when heated at zero load in the second thermomechanical cycle, and a stress recovery of 1.5-4.2 MPa was observed for the constrained displacement recovery experiments. After the experiments were performed, the Chen and Lagoudas model was used to simulate and predict the experimental results. The material properties used in the constitutive model—namely the coefficients of thermal expansion, shear moduli, and frozen volume fraction—were calibrated from a single 10% extension free recovery experiment. The model was then used to predict the material response for the remaining free recovery and constrained displacement recovery experiments. The model predictions match well with the experimental data.

Dynamics of Model Hydraulic Fracturing Liquid Studied by Two-Dimensional Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Daley, Kim; Kubarych, Kevin J.

2014-06-01

The technique of two-dimensional infrared (2DIR) spectroscopy is used to expose the chemical dynamics of various concentrations of polymers and their monomers in heterogeneous mixtures. An environmentally relevant heterogeneous mixture, which inspires this study, is hydraulic fracturing liquid (HFL). Hydraulic fracking is a technique used to extract natural gas from shale deposits. HFL consists of mostly water, proppant (sand), an emulsifier (guar), and other chemicals specific to the drilling site. Utilizing a metal carbonyl as a probe, we observe the spectral dynamics of the polymer, guar, and its monomer, mannose, and compare the results to see how hydration dynamics change with varying concentration. Another polymer, Ficoll, and its monomer, sucrose, are also compared to see how polymer size affects hydration dynamics. The two results are as follows: (1) Guar experiences collective hydration at high concentrations, where as mannose experiences independent hydration; (2) no collective hydration is observed for Ficoll in the same concentration range as guar, possibly due to polymer shape and size. HFL experiences extremely high pressure during natural gas removal, so future studies will focus on how increased pressure affects the hydration dynamics of polymers and monomers.

A density functional approach to ferrogels

NASA Astrophysics Data System (ADS)

Cremer, P.; Heinen, M.; Menzel, A. M.; Löwen, H.

2017-07-01

Ferrogels consist of magnetic colloidal particles embedded in an elastic polymer matrix. As a consequence, their structural and rheological properties are governed by a competition between magnetic particle-particle interactions and mechanical matrix elasticity. Typically, the particles are permanently fixed within the matrix, which makes them distinguishable by their positions. Over time, particle neighbors do not change due to the fixation by the matrix. Here we present a classical density functional approach for such ferrogels. We map the elastic matrix-induced interactions between neighboring colloidal particles distinguishable by their positions onto effective pairwise interactions between indistinguishable particles similar to a ‘pairwise pseudopotential’. Using Monte-Carlo computer simulations, we demonstrate for one-dimensional dipole-spring models of ferrogels that this mapping is justified. We then use the pseudopotential as an input into classical density functional theory of inhomogeneous fluids and predict the bulk elastic modulus of the ferrogel under various conditions. In addition, we propose the use of an ‘external pseudopotential’ when one switches from the viewpoint of a one-dimensional dipole-spring object to a one-dimensional chain embedded in an infinitely extended bulk matrix. Our mapping approach paves the way to describe various inhomogeneous situations of ferrogels using classical density functional concepts of inhomogeneous fluids.

Percolated microstructures for multi-modal transport enhancement in porous active materials

DOEpatents

McKay, Ian Salmon; Yang, Sungwoo; Wang, Evelyn N.; Kim, Hyunho

2018-03-13

A method of forming a composite material for use in multi-modal transport includes providing three-dimensional graphene having hollow channels, enabling a polymer to wick into the hollow channels of the three-dimensional graphene, curing the polymer to form a cured three-dimensional graphene, adding an active material to the cured three-dimensional graphene to form a composite material, and removing the polymer from within the hollow channels. A composite material formed according to the method is also provided.

Three-dimensional smoothed particle hydrodynamics simulation for injection molding flow of short fiber-reinforced polymer composites

NASA Astrophysics Data System (ADS)

He, Liping; Lu, Gang; Chen, Dachuan; Li, Wenjun; Lu, Chunsheng

2017-07-01

This paper investigates the three-dimensional (3D) injection molding flow of short fiber-reinforced polymer composites using a smoothed particle hydrodynamics (SPH) simulation method. The polymer melt was modeled as a power law fluid and the fibers were considered as rigid cylindrical bodies. The filling details and fiber orientation in the injection-molding process were studied. The results indicated that the SPH method could effectively predict the order of filling, fiber accumulation, and heterogeneous distribution of fibers. The SPH simulation also showed that fibers were mainly aligned to the flow direction in the skin layer and inclined to the flow direction in the core layer. Additionally, the fiber-orientation state in the simulation was quantitatively analyzed and found to be consistent with the results calculated by conventional tensor methods.

Simple model of sickle hemogloblin

NASA Astrophysics Data System (ADS)

Shiryayev, Andrey; Li, Xiaofei; Gunton, J. D.

2006-07-01

A microscopic model is proposed for the interactions between sickle hemoglobin molecules based on information from the protein data bank. A solution of this model, however, requires accurate estimates of the interaction parameters which are currently unavailable. Therefore, as a first step toward a molecular understanding of the nucleation mechanisms in sickle hemoglobin, a Monte Carlo simulation of a simplified two patch model is carried out. A gradual transition from monomers to one dimensional chains is observed as one varies the density of molecules at fixed temperature, somewhat similar to the transition from monomers to polymer fibers in sickle hemoglobin molecules in solution. An observed competition between chain formation and crystallization for the model is also discussed. The results of the simulation of the equation of state are shown to be in excellent agreement with a theory for a model of globular proteins, for the case of two interacting sites.

One Dimensional Coordination Polymer of Zn(II) for Developing Multifunctional Nanoparticles.

PubMed

Agarwal, Rashmi A

2017-10-16

A variety of nanoparticles (NPs) including Ag, Au, Pd, Cr and mixed Cu/Fe have been synthesized in a non-activated (without solvent removal) one dimensional coordination polymer (CP) of Zn(II) via two different mechanisms, acid formation and redox activity of the framework. Main driving force to grow these NPs within the cavities of CP is the presence of free oxygens of one of the monodentate carboxylate groups of BDC ligand. These free oxygens act as anchoring sites for the metal ions of the metal precursors. Chemical and physical characteristics of the NPs within the framework have been evaluated by the high resolution transmission electron microscopic (HRTEM) images. Excluding Ag(0) and Pd(0) other NPs are present as combinations of their elemental as well as oxide forms (Au/Au 2 O 3 , Cr/Cr 2 O 3 /CrO 2 and Cu/Cu 2 O, Fe/FeO). Synthesized Ag NPs within the framework show remarkable antibacterial efficacy at extremely low concentrations. Ag, Au and Cu/Fe NPs show ferromagnetic properties within the framework at room temperature. This polymer has potential to sequester highly toxic Cr(VI) to non toxic Cr(0), Cr(III) and Cr(IV) species.

Polymerization of a divalent/tetravalent metal-storing atom-mimicking dendrimer.

PubMed

Albrecht, Ken; Hirabayashi, Yuki; Otake, Masaya; Mendori, Shin; Tobari, Yuta; Azuma, Yasuo; Majima, Yutaka; Yamamoto, Kimihisa

2016-12-01

The phenylazomethine dendrimer (DPA) has a layer-by-layer electron density gradient that is an analog of the Bohr atom (atom mimicry). In combination with electron pair mimicry, the polymerization of this atom-mimicking dendrimer was achieved. The valency of the mimicked atom was controlled by changing the chemical structure of the dendrimer. By mimicking a divalent atom, a one-dimensional (1D) polymer was obtained, and by using a planar tetravalent atom mimic, a 2D polymer was obtained. These poly(dendrimer) polymers could store Lewis acids (SnCl 2 ) in their unoccupied orbitals, thus indicating that these poly(dendrimer) polymers consist of a series of nanocontainers.

Mechanistic modeling of modular co-rotating twin-screw extruders.

PubMed

Eitzlmayr, Andreas; Koscher, Gerold; Reynolds, Gavin; Huang, Zhenyu; Booth, Jonathan; Shering, Philip; Khinast, Johannes

2014-10-20

In this study, we present a one-dimensional (1D) model of the metering zone of a modular, co-rotating twin-screw extruder for pharmaceutical hot melt extrusion (HME). The model accounts for filling ratio, pressure, melt temperature in screw channels and gaps, driving power, torque and the residence time distribution (RTD). It requires two empirical parameters for each screw element to be determined experimentally or numerically using computational fluid dynamics (CFD). The required Nusselt correlation for the heat transfer to the barrel was determined from experimental data. We present results for a fluid with a constant viscosity in comparison to literature data obtained from CFD simulations. Moreover, we show how to incorporate the rheology of a typical, non-Newtonian polymer melt, and present results in comparison to measurements. For both cases, we achieved excellent agreement. Furthermore, we present results for the RTD, based on experimental data from the literature, and found good agreement with simulations, in which the entire HME process was approximated with the metering model, assuming a constant viscosity for the polymer melt. Copyright © 2014. Published by Elsevier B.V.

Polymer Crowding in Confined Polymer-Nanoparticle Mixtures

NASA Astrophysics Data System (ADS)

Davis, Wyatt J.; Denton, Alan R.

Crowding can influence the conformations and thus functionality of macromolecules in quasi-two-dimensional environments, such as DNA or proteins confined to a cell membrane. We explore such crowding within a model of polymers as penetrable ellipses, whose shapes are governed by the statistics of a 2D random walk. The principal radii of the polymers fluctuate according to probability distributions of the eigenvalues of the gyration tensor. Within this coarse-grained model, we perform Monte Carlo simulations of mixtures of polymers and hard nanodisks, including trial changes in polymer conformation (shape and orientation). Penetration of polymers by nanodisks is incorporated with a free energy cost predicted by polymer field theory. Over ranges of size ratio and nanodisk density, we analyze the influence of crowding on polymer shape by computing eigenvalue distributions, mean radius of gyration, and mean asphericity of the polymer. We compare results with predictions of free-volume theory and with corresponding results in three dimensions. Our approach may help to interpret recent (and motivate future) experimental studies of biopolymers interacting with cell membranes, with relevance for drug delivery and gene therapy. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

Optimizing separations in online comprehensive two-dimensional liquid chromatography.

PubMed

Pirok, Bob W J; Gargano, Andrea F G; Schoenmakers, Peter J

2018-01-01

Online comprehensive two-dimensional liquid chromatography has become an attractive option for the analysis of complex nonvolatile samples found in various fields (e.g. environmental studies, food, life, and polymer sciences). Two-dimensional liquid chromatography complements the highly popular hyphenated systems that combine liquid chromatography with mass spectrometry. Two-dimensional liquid chromatography is also applied to the analysis of samples that are not compatible with mass spectrometry (e.g. high-molecular-weight polymers), providing important information on the distribution of the sample components along chemical dimensions (molecular weight, charge, lipophilicity, stereochemistry, etc.). Also, in comparison with conventional one-dimensional liquid chromatography, two-dimensional liquid chromatography provides a greater separation power (peak capacity). Because of the additional selectivity and higher peak capacity, the combination of two-dimensional liquid chromatography with mass spectrometry allows for simpler mixtures of compounds to be introduced in the ion source at any given time, improving quantitative analysis by reducing matrix effects. In this review, we summarize the rationale and principles of two-dimensional liquid chromatography experiments, describe advantages and disadvantages of combining different selectivities and discuss strategies to improve the quality of two-dimensional liquid chromatography separations. © 2017 The Authors. Journal of Separation Science published by WILEY-VCH Verlag GmbH & Co. KGaA.

Microfabrication and Test of a Three-Dimensional Polymer Hydro-focusing Unit for Flow Cytometry Applications

NASA Technical Reports Server (NTRS)

Yang, Ren; Feeback, Daniel L.; Wang, Wan-Jun

2005-01-01

This paper details a novel three-dimensional (3D) hydro-focusing micro cell sorter for micro flow cytometry applications. The unit was microfabricated by means of SU-8 3D lithography. The 3D microstructure for coaxial sheathing was designed, microfabricated, and tested. Three-dimensional hydrofocusing capability was demonstrated with an experiment to sort labeled tanned sheep erythrocytes (red blood cells). This polymer hydro-focusing microstructure is easily microfabricated and integrated with other polymer microfluidic structures. Keywords: SU-8, three-dimensional hydro-focusing, microfluidic, microchannel, cytometer

(U) A Gruneisen Equation of State for TPX. Application in FLAG

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

Fredenburg, David A.; Aslam, Tariq Dennis; Bennett, Langdon Stanford

2015-11-02

A Gruneisen equation of state (EOS) is developed for the polymer TPX (poly 4-methyl-1-pentene) within the LANL hydrocode FLAG. Experimental shock Hugoniot data for TPX is fit to a form of the Gruneisen EOS, and the necessary parameters for implementing the TPX EOS in FLAG are presented. The TPX EOS is further validated through one-dimensional simulations of recent double-shock experiments, and a comparison is made between the new Gruneisen EOS for TPX and the EOS representation for TPX used in the LANL Common Model.

Chemical colloids versus biological colloids: a comparative study for the elucidation of the mechanism of protein fiber formation

NASA Technical Reports Server (NTRS)

Xu, Shaohua; Wu, David; Arnsdorf, Morton; Johnson, Robert; Getz, Godfrey S.; Cabana, Veneracion G.

2005-01-01

Fiber formation from murine serum amyloid A1 (SAA) was compared to the linear aggregation and fiber formation of colloidal gold particles. Here we report the similarities of these processes. Upon incubation with acetic acid, SAA misfolds and adopts a new conformation, which we termed saa. saa apparently is less soluble than SAA in aqueous solution; it aggregates and forms nucleation units and then fibers. The fibers appear as a string of the nucleation units. Additionally, an external electric field promotes saa fiber formation. These properties of saa are reminiscent of colloidal gold formation from gold ions and one-dimensional aggregation of the gold colloids. Colloidal gold particles were also found to be capable of aggregating one-dimensionally under an electric field or in the presence of polylysine. These gold fibers resembled in structure that of saa fibers. In summary, protein aggregation and formation of fibers appear to follow the generalized principles derived in colloidal science for the aggregation of atoms and molecules, including polymers such as polypeptides. The analysis of colloidal gold formation and of one-dimensional aggregation provides a simple model system for the elucidation of some aspects of protein fiber formation.

Characterizing and modeling the free recovery and constrained recovery behavior of a polyurethane shape memory polymer

PubMed Central

Volk, Brent L; Lagoudas, Dimitris C; Maitland, Duncan J

2011-01-01

In this work, tensile tests and one-dimensional constitutive modeling are performed on a high recovery force polyurethane shape memory polymer that is being considered for biomedical applications. The tensile tests investigate the free recovery (zero load) response as well as the constrained displacement recovery (stress recovery) response at extension values up to 25%, and two consecutive cycles are performed during each test. The material is observed to recover 100% of the applied deformation when heated at zero load in the second thermomechanical cycle, and a stress recovery of 1.5 MPa to 4.2 MPa is observed for the constrained displacement recovery experiments. After performing the experiments, the Chen and Lagoudas model is used to simulate and predict the experimental results. The material properties used in the constitutive model – namely the coefficients of thermal expansion, shear moduli, and frozen volume fraction – are calibrated from a single 10% extension free recovery experiment. The model is then used to predict the material response for the remaining free recovery and constrained displacement recovery experiments. The model predictions match well with the experimental data. PMID:22003272

A theoretical framework for the study of compression sensing in ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Volpini, Valentina; Bardella, Lorenzo; Rodella, Andrea; Cha, Youngsu; Porfiri, Maurizio

2017-04-01

Ionic Polymer Metal Composites (IPMCs) are electro-responsive materials for sensing and actuation, consisting of an ion-exchange polymeric membrane with ionized units, plated within noble metal electrodes. In this work, we investigate the sensing response of IPMCs that are subject to a through-the-thickness compression, by specializing the continuum model introduced by Cha and Porfiri,1 to this one-dimensional problem. This model modifies the classical Poisson-Nernst-Plank system governing the electrochemistry in the absence of mechanical effects, by accounting for finite deformations underlying the actuation and sensing processes. With the aim of accurately describing the IPMC dynamic compressive behavior, we introduce a spatial asymmetry in the properties of the membrane, which must be accounted for to trigger a sensing response. Then, we determine an analytical solution by applying the singular perturbation theory, and in particular the method of matched asymptotic expansions. This solution shows a good agreement with experimental findings reported in literature.

Non-isothermal two-phase transport in the polymer electrolyte membrane fuel cell microporous layer

NASA Astrophysics Data System (ADS)

Ge, Nan

This thesis investigates the water transport mechanisms in the crack-free microporous layer (MPL) of a polymer electrolyte membrane (PEM) fuel cell. Synchrotron X-ray radiography was used to visualize and quantify the in situ liquid water in the gas diffusion layers (GDLs) of an operating fuel cell. A methodology was developed to correct the artefact of imaging sample movement. Furthermore, to address inaccuracies due to the scattering effect and higher harmonics at the synchrotron beamline, a calibration technique was introduced in order to experimentally determine the liquid water X-ray attenuation coefficient. Through in situ radiography, liquid water breakthrough events were observed in the MPL, and measured water thicknesses were used as inputs into a one-dimensional (1D) heat and mass transport model. The 1D model was used to describe the coupled relationship between liquid and vapour transport through the cathode MPL and the temperature distributions in the operating fuel cell.

Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space.

PubMed

Rebollar, Esther; Pérez, Susana; Hernández, Jaime J; Martín-Fabiani, Ignacio; Rueda, Daniel R; Ezquerra, Tiberio A; Castillejo, Marta

2011-05-03

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.

Translating textiles to tissue engineering: Creation and evaluation of microporous, biocompatible, degradable scaffolds using industry relevant manufacturing approaches and human adipose derived stem cells.

PubMed

Haslauer, Carla M; Avery, Matthew R; Pourdeyhimi, Behnam; Loboa, Elizabeth G

2015-07-01

Polymeric scaffolds have emerged as a means of generating three-dimensional tissues, such as for the treatment of bone injuries and nonunions. In this study, a fibrous scaffold was designed using the biocompatible, degradable polymer poly-lactic acid in combination with a water dispersible sacrificial polymer, EastONE. Fibers were generated via industry relevant, facile scale-up melt-spinning techniques with an islands-in-the-sea geometry. Following removal of EastONE, a highly porous fiber remained possessing 12 longitudinal channels and pores throughout all internal and external fiber walls. Weight loss and surface area characterization confirmed the generation of highly porous fibers as observed via focused ion beam/scanning electron microscopy. Porous fibers were then knit into a three-dimensional scaffold and seeded with human adipose-derived stem cells (hASC). Confocal microscopy images confirmed hASC attachment to the fiber walls and proliferation throughout the knit structure. Quantification of cell-mediated calcium accretion following culture in osteogenic differentiation medium confirmed hASC differentiation throughout the porous constructs. These results suggest incorporation of a sacrificial polymer within islands-in-the-sea fibers generates a highly porous scaffold capable of supporting stem cell viability and differentiation with the potential to generate large three-dimensional constructs for bone regeneration and/or other tissue engineering applications. © 2014 Wiley Periodicals, Inc.

Introduction

NASA Astrophysics Data System (ADS)

Bouma, Brett E.

1998-09-01

The pace of technological advancement of Optical Coherence Tomography (OCT) over the last several years has been extremely rapid. The field has progressed from one-dimensional low-coherence ranging to full three-dimensional imaging with individual two-dimensional images aquired at near video rate in a span of less than eight years. Imaging applications have included polymers and advanced composites, Ophthalmology, Developmental Biology, Gastroenterology, Urology, Cardiology, Neurology, and Gynecology. These preliminary studies indicate the great potential for OCT to make a significant impact, especially in clinical medicine.

Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

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

Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li

2013-09-15

Three new metal-organic coordination polymers [Co(4-bbc){sub 2}(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H{sub 2}O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H{sub 2}pdc=3,5-pyridinedicarboxylic acid, 1,4-H{sub 2}ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co{sup II} ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3{sup 2}·4·5·6{sup 2}·7{sup 4}) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphicalmore » abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated.« less

Electrospinning bioactive supramolecular polymers from water.

PubMed

Tayi, Alok S; Pashuck, E Thomas; Newcomb, Christina J; McClendon, Mark T; Stupp, Samuel I

2014-04-14

Electrospinning is a high-throughput, low-cost technique for manufacturing long fibers from solution. Conventionally, this technique is used with covalent polymers with large molecular weights. We report here the electrospinning of functional peptide-based supramolecular polymers from water at very low concentrations (<4 wt %). Molecules with low molecular weights (<1 kDa) could be electrospun because they self-assembled into one-dimensional supramolecular polymers upon solvation and the critical parameters of viscosity, solution conductivity, and surface tension were optimized for this technique. The supramolecular structure of the electrospun fibers could ensure that certain residues, like bioepitopes, are displayed on the surface even after processing. This system provides an opportunity to electrospin bioactive supramolecular materials from water for biomedical applications.

Effect of multi-dimensional ultraviolet light exposure on the growth of pentacene film and application to organic field-effect transistors.

PubMed

Bae, Jin-Hyuk; Lee, Sin-Doo; Choi, Jong Sun; Park, Jaehoon

2012-05-01

We report on the multi-dimensional alignment of pentacene molecules on a poly(methyl methacrylate)-based photosensitive polymer (PMMA-polymer) and its effect on the electrical performance of the pentacene-based field-effect transistor (FET). Pentacene molecules are shown to be preferentially aligned on the linearly polarized ultraviolet (LPUV)-exposed PMMA-polymer layer, which is contrast to an isotropic alignment on the bare PMMA-polymer layer. Multi-dimensional alignment of pentacene molecules in the film could be achieved by adjusting the direction of LPUV exposed to the PMMA-polymer. The control of pentacene molecular alignment is found to be promising for the field-effect mobility enhancement in the pentacene FET.

One- and two-dimensional divalent copper coordination polymers based on kinked organodiimine and long flexible aliphatic dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Mallika Krishnan, Subhashree; Supkowski, Ronald M.; LaDuca, Robert L.

2008-11-01

Hydrothermal synthesis under acidic conditions has afforded a pair of divalent copper coordination polymers containing the kinked dipodal tethering organodiimine 4,4'-dipyridylamine (dpa) and flexible long-chain aliphatic dicarboxylate ligands. The new materials were characterized by single crystal X-ray structure determination, infrared spectroscopy, and thermogravimetric analysis. [CuCl(suberate) 0.5(dpa)] ( 1) manifests 1-D ladder-like motifs aggregated into 3-D through hydrogen bonding and copper-mediated supramolecular interactions. Extension of the aliphatic chain within the dicarboxylate ligand by one methylene unit resulted in {[Cu(azelate)(dpa)(H 2O)] · 3H 2O} ( 2), a (4,4) rhomboid grid 2-D coordination polymer encapsulating acyclic water molecule trimers.

Air and moisture stable covalently-bonded tin(ii) coordination polymers.

PubMed

de Lima, G M; Walton, R I; Clarkson, G J; Bitzer, R S; Ardisson, J D

2018-06-05

Four covalently-bonded tin(ii) coordination polymers, (1)-(4), were hydrothermally prepared in aqueous alkaline media by the reactions of SnSO4 with 1,2,4,5-benzenetetracarboxylic acid (1), 1,3,5-benzenetricarboxylic acid (2), 4-hydroxypyridine-2,6-dicarboxylic acid (3), and 1,3,5-cyclohexanetricarboxylic acid (4). All products were structurally authenticated by single-crystal X-ray diffraction, and the number of different tin centres and their oxidation states were confirmed by 119Sn Mössbauer spectroscopy. In addition, the comparison between experimental and simulated X-ray powder diffraction patterns confirmed the authenticity of the samples. Our crystallographic results for (1)-(4) show that the Sn(ii) centres are tetracoordinated and exhibit distorted disphenoidal geometries, corroborating the presence of one stereochemically active lone electron pair at each metal site. Products (1) and (2) display bi-dimensional polymeric structures, (3) exhibits a one-dimensional architecture, whereas (4) shows a remarkable three-dimensional coordination network. Hirshfeld surface and supramolecular analyses for the repeating units of (1)-(4) were also performed in order to identify structurally important non-covalent interactions.

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

NASA Astrophysics Data System (ADS)

Steiner, Christian; Gebhardt, Julian; Ammon, Maximilian; Yang, Zechao; Heidenreich, Alexander; Hammer, Natalie; Görling, Andreas; Kivala, Milan; Maier, Sabine

2017-03-01

The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π-conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

Structure and topology of three-dimensional hydrocarbon polymers.

PubMed

Kondrin, Mikhail V; Lebed, Yulia B; Brazhkin, Vadim V

2016-08-01

A new family of three-dimensional hydrocarbon polymers which are more energetically favorable than benzene is proposed. Although structurally these polymers are closely related to well known diamond and lonsdaleite carbon structures, using topological arguments we demonstrate that they have no known structural analogs. Topological considerations also give some indication of possible methods of synthesis. Taking into account their exceptional optical, structural and mechanical properties these polymers might have interesting applications.

Two-dimensional correlation spectroscopy in polymer study

PubMed Central

Park, Yeonju; Noda, Isao; Jung, Young Mee

2015-01-01

This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation. The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted. PMID:25815286

Nonequilibrium Statistical Mechanics in One Dimension

NASA Astrophysics Data System (ADS)

Privman, Vladimir

2005-08-01

Part I. Reaction-Diffusion Systems and Models of Catalysis; 1. Scaling theories of diffusion-controlled and ballistically-controlled bimolecular reactions S. Redner; 2. The coalescence process, A+A->A, and the method of interparticle distribution functions D. ben-Avraham; 3. Critical phenomena at absorbing states R. Dickman; Part II. Kinetic Ising Models; 4. Kinetic ising models with competing dynamics: mappings, correlations, steady states, and phase transitions Z. Racz; 5. Glauber dynamics of the ising model N. Ito; 6. 1D Kinetic ising models at low temperatures - critical dynamics, domain growth, and freezing S. Cornell; Part III. Ordering, Coagulation, Phase Separation; 7. Phase-ordering dynamics in one dimension A. J. Bray; 8. Phase separation, cluster growth, and reaction kinetics in models with synchronous dynamics V. Privman; 9. Stochastic models of aggregation with injection H. Takayasu and M. Takayasu; Part IV. Random Sequential Adsorption and Relaxation Processes; 10. Random and cooperative sequential adsorption: exactly solvable problems on 1D lattices, continuum limits, and 2D extensions J. W. Evans; 11. Lattice models of irreversible adsorption and diffusion P. Nielaba; 12. Deposition-evaporation dynamics: jamming, conservation laws and dynamical diversity M. Barma; Part V. Fluctuations In Particle and Surface Systems; 13. Microscopic models of macroscopic shocks S. A. Janowsky and J. L. Lebowitz; 14. The asymmetric exclusion model: exact results through a matrix approach B. Derrida and M. R. Evans; 15. Nonequilibrium surface dynamics with volume conservation J. Krug; 16. Directed walks models of polymers and wetting J. Yeomans; Part VI. Diffusion and Transport In One Dimension; 17. Some recent exact solutions of the Fokker-Planck equation H. L. Frisch; 18. Random walks, resonance, and ratchets C. R. Doering and T. C. Elston; 19. One-dimensional random walks in random environment K. Ziegler; Part VII. Experimental Results; 20. Diffusion-limited exciton kinetics in one-dimensional systems R. Kroon and R. Sprik; 21. Experimental investigations of molecular and excitonic elementary reaction kinetics in one-dimensional systems R. Kopelman and A. L. Lin; 22. Luminescence quenching as a probe of particle distribution S. H. Bossmann and L. S. Schulman; Index.

Parametric modeling of wideband piezoelectric polymer sensors: Design for optoacoustic applications

NASA Astrophysics Data System (ADS)

Fernández Vidal, A.; Ciocci Brazzano, L.; Matteo, C. L.; Sorichetti, P. A.; González, M. G.

2017-09-01

In this work, we present a three-dimensional model for the design of wideband piezoelectric polymer sensors which includes the geometry and the properties of the transducer materials. The model uses FFT and numerical integration techniques in an explicit, semi-analytical approach. To validate the model, we made electrical and mechanical measurements on homemade sensors for optoacoustic applications. Each device was implemented using a polyvinylidene fluoride thin film piezoelectric polymer with a thickness of 25 μm. The sensors had detection areas in the range between 0.5 mm2 and 35 mm2 and were excited by acoustic pressure pulses of 5 ns (FWHM) from a source with a diameter around 10 μm. The experimental data obtained from the measurements agree well with the model results. We discuss the relative importance of the sensor design parameters for optoacoustic applications and we provide guidelines for the optimization of devices.

Parametric modeling of wideband piezoelectric polymer sensors: Design for optoacoustic applications.

PubMed

Fernández Vidal, A; Ciocci Brazzano, L; Matteo, C L; Sorichetti, P A; González, M G

2017-09-01

In this work, we present a three-dimensional model for the design of wideband piezoelectric polymer sensors which includes the geometry and the properties of the transducer materials. The model uses FFT and numerical integration techniques in an explicit, semi-analytical approach. To validate the model, we made electrical and mechanical measurements on homemade sensors for optoacoustic applications. Each device was implemented using a polyvinylidene fluoride thin film piezoelectric polymer with a thickness of 25 μm. The sensors had detection areas in the range between 0.5 mm 2 and 35 mm 2 and were excited by acoustic pressure pulses of 5 ns (FWHM) from a source with a diameter around 10 μm. The experimental data obtained from the measurements agree well with the model results. We discuss the relative importance of the sensor design parameters for optoacoustic applications and we provide guidelines for the optimization of devices.

Modeling the pyrolysis study of non-charring polymers under reduced pressure environments

NASA Astrophysics Data System (ADS)

Zong, Ruowen; Kang, Ruxue; Hu, Yanghui; Zhi, Youran

2018-04-01

In order to study the pyrolysis of non-charring polymers under reduced pressure environments, a series of experiments based on black acrylonitrile butadiene styrene (ABS) was conducted in a reduced pressure chamber under different external heat fluxes. The temperatures of the top surface and the bottom of the sample and the mass loss during the whole process were measured in real time. A one-dimensional numerical model was developed to predict the top surface and the bottom surface temperatures of ABS during the pyrolysis at different reduced pressures and external heat fluxes, and the model was validated by the experimental data. The results of the study indicate that the profiles of the top surface and the bottom surface temperatures are different at different pressures and heat fluxes. The temperature and the mass loss rate of the sample under a lower heat flux decreased significantly as the pressure was increased. However, under a higher heat flux, the temperature and the mass loss rate showed little sensitivity to the pressure. The simulated results fitted the experimental results better at the higher heat flux than at the lower heat flux.

Three-dimensional iron(ii) porous coordination polymer exhibiting carbon dioxide-dependent spin crossover.

PubMed

Shin, Jong Won; Jeong, Ah Rim; Jeoung, Sungeun; Moon, Hoi Ri; Komatsumaru, Yuki; Hayami, Shinya; Moon, Dohyun; Min, Kil Sik

2018-04-24

We report a three-dimensional Fe(ii) porous coordination polymer that exhibits a spin crossover temperature change following CO2 sorption (though not N2 sorption). Furthermore, single crystals of the desolvated polymer with CO2 molecules at three different temperatures were characterised by X-ray crystallography.

Holographically Fabricated Photonic Crystals with Large Reflectance

DTIC Science & Technology

2008-07-16

CLASSIFICATION OF: We report reflection and transmission spectra from three-dimensional polymer photonic crystals fabricated by holographic...transmission spectra from three-dimensional polymer photonic crystals fabricated by holographic lithography. The measured peak reflectance matches that... polymer photonic crystals fabricated by holographic lithography. The measured peak reflectance matches that predicted by both a finite-difference time

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2002-01-01

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Conducting polymer nanostructures for photocatalysis under visible light

NASA Astrophysics Data System (ADS)

Ghosh, Srabanti; Kouamé, Natalie A.; Ramos, Laurence; Remita, Samy; Dazzi, Alexandre; Deniset-Besseau, Ariane; Beaunier, Patricia; Goubard, Fabrice; Aubert, Pierre-Henri; Remita, Hynd

2015-05-01

Visible-light-responsive photocatalysts can directly harvest energy from solar light, offering a desirable way to solve energy and environment issues. Here, we show that one-dimensional poly(diphenylbutadiyne) nanostructures synthesized by photopolymerization using a soft templating approach have high photocatalytic activity under visible light without the assistance of sacrificial reagents or precious metal co-catalysts. These polymer nanostructures are very stable even after repeated cycling. Transmission electron microscopy and nanoscale infrared characterizations reveal that the morphology and structure of the polymer nanostructures remain unchanged after many photocatalytic cycles. These stable and cheap polymer nanofibres are easy to process and can be reused without appreciable loss of activity. Our findings may help the development of semiconducting-based polymers for applications in self-cleaning surfaces, hydrogen generation and photovoltaics.

A novel multiphysic model for simulation of swelling equilibrium of ionized thermal-stimulus responsive hydrogels

NASA Astrophysics Data System (ADS)

Li, Hua; Wang, Xiaogui; Yan, Guoping; Lam, K. Y.; Cheng, Sixue; Zou, Tao; Zhuo, Renxi

2005-03-01

In this paper, a novel multiphysic mathematical model is developed for simulation of swelling equilibrium of ionized temperature sensitive hydrogels with the volume phase transition, and it is termed the multi-effect-coupling thermal-stimulus (MECtherm) model. This model consists of the steady-state Nernst-Planck equation, Poisson equation and swelling equilibrium governing equation based on the Flory's mean field theory, in which two types of polymer-solvent interaction parameters, as the functions of temperature and polymer-network volume fraction, are specified with or without consideration of the hydrogen bond interaction. In order to examine the MECtherm model consisting of nonlinear partial differential equations, a meshless Hermite-Cloud method is used for numerical solution of one-dimensional swelling equilibrium of thermal-stimulus responsive hydrogels immersed in a bathing solution. The computed results are in very good agreements with experimental data for the variation of volume swelling ratio with temperature. The influences of the salt concentration and initial fixed-charge density are discussed in detail on the variations of volume swelling ratio of hydrogels, mobile ion concentrations and electric potential of both interior hydrogels and exterior bathing solution.

Microfabrication and Test of a Three-Dimensional Polymer Hydro-focusing Unit for Flow Cytometry Applications

NASA Technical Reports Server (NTRS)

Yang, Ren; Feeback, Daniel L.; Wang, Wanjun

2004-01-01

This paper details a novel three-dimensional (3D) hydro-focusing micro cell sorter for micro flow cytometry applications. The unit was microfabricated by means of SU-8 3D lithography. The 3D microstructure for coaxial sheathing was designed, microfabricated, and tested. Three-dimensional hydro-focusing capability was demonstrated with an experiment to sort labeled tanned sheep erythrocytes (red blood cells). This polymer hydro-focusing microstructure is easily microfabricated and integrated with other polymer microfluidic structures.

Microfabrication and Test of a Three-Dimensional Polymer Hydro-Focusing Unit for Flow Cytometry Applications

NASA Technical Reports Server (NTRS)

Yang, Ren; Feedback, Daniel L.; Wang, Wanjun

2004-01-01

This paper details a novel three-dimensional (3D) hydro-focusing micro cell sorter for micro flow cytometry applications. The unit was micro-fabricated by means of SU-8 3D lithography. The 3D microstructure for coaxial sheathing was designed, micro-fabricated, and tested. Three-dimensional hydrofocusing capability was demonstrated with an experiment to sort labeled tanned sheep erythrocytes (red blood cells). This polymer hydro-focusing microstructure is easily micro-fabricated and integrated with other polymer microfluidic structures.

A modified dynamical model of drying process of polymer blend solution coated on a flat substrate

NASA Astrophysics Data System (ADS)

Kagami, Hiroyuki

2008-05-01

We have proposed and modified a model of drying process of polymer solution coated on a flat substrate for flat polymer film fabrication. And for example numerical simulation of the model reproduces a typical thickness profile of the polymer film formed after drying. Then we have clarified dependence of distribution of polymer molecules on a flat substrate on a various parameters based on analysis of numerical simulations. Then we drove nonlinear equations of drying process from the dynamical model and the fruits were reported. The subject of above studies was limited to solution having one kind of solute though the model could essentially deal with solution having some kinds of solutes. But nowadays discussion of drying process of a solution having some kinds of solutes is needed because drying process of solution having some kinds of solutes appears in many industrial scenes. Polymer blend solution is one instance. And typical resist consists of a few kinds of polymers. Then we introduced a dynamical model of drying process of polymer blend solution coated on a flat substrate and results of numerical simulations of the dynamical model. But above model was the simplest one. In this study, we modify above dynamical model of drying process of polymer blend solution adding effects that some parameters change with time as functions of some variables to it. Then we consider essence of drying process of polymer blend solution through comparison between results of numerical simulations of the modified model and those of the former model.

Synthesis, crystal structures and luminescent properties of two 4 d-4 f Ln-Ag heterometallic coordination polymers based on anion template

NASA Astrophysics Data System (ADS)

Fan, Le-Qing; Chen, Yuan; Wu, Ji-Huai; Huang, Yun-Fang

2011-04-01

Two new 4 d-4 f Ln-Ag heterometallic coordination polymers, {[ Ln3Ag 5(IN) 10(H 2O) 7]·4(ClO 4)·4(H 2O)} n ( Ln=Eu ( 1) and Sm ( 2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions by reactions of Ln2O 3, AgNO 3, HIN and HClO 4, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. It is proved that HClO 4 not only adjusts the pH value of the reaction mixture, but also acts as anion template. The structure determination reveals that 1 and 2 are isostructural and feature a novel two-dimensional (2D) layered hetrometallic structure constructed from one-dimensional Ln-carboxylate chains and pillared Ag(IN) 2 units. The 2D layers are further interlinked through Ag⋯Ag and Ag⋯O(ClO 4-) multiple weak interactions, which form a rare Ag-ClO 4 ribbon in lanthanide-transition metal coordination polymers, to give rise to a three-dimensional supramolecular architecture. Moreover, the luminescent properties of these two compounds have also been investigated at room temperature.

Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds—synthesis, X-Ray studies and magnetic properties

NASA Astrophysics Data System (ADS)

Machura, B.; Świtlicka, A.; Zwoliński, P.; Mroziński, J.; Kalińska, B.; Kruszynski, R.

2013-01-01

Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH)4Hg(SCN)4]n (1) [Cu(indH)4Hg(SCN)4]n (2) and [Cu(ampy)2Hg(SCN)4]n (3), have one-dimensional coordination structure. Two compounds [Cu(pzH)2Hg(SCN)4]n (4) and [Cu(abzimH)Hg(SCN)4]n (5) form two-dimensional nets, whereas the complexes [Cu(pyCN)2Hg(SCN)4]n (6) and [Cu(pyCH(OH)(OMe))2Hg(SCN)4]n (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net. In 2 the N-H•••S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H•••N and N-H•••S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net.

A new Pb{sup II}(ethylenediaminetetraacetate) coordination polymer with a two-dimensional layer structure

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

Zhao, D., E-mail: iamzd@hpu.edu.cn; Zhang, R. H.; Li, F. F.

2016-12-15

A new Pb{sup II}−edta{sup 4–} coordination polymer, Pb{sub 2}(edta)(H{sub 2}O){sub 0.76} (edta{sup 4–} = ethylenediaminetetraacetate) was synthesized under hydrothermal condition. Single crystal X-ray analysis reveals that it represents a novel two-dimensional (2D) Pb{sup 2+}–edta{sup 4–} layer structure with a (4,8{sup 2})-topology. Each edta{sup 4–} ligand employs its four carboxylate O and two N atoms to chelate one Pb{sup II} atom (hexa-coordinated) and connects five Pb{sup II} atoms (ennea-coordinated) via its four carboxylate groups to form 2D layer framework. Adjacent layers are packed into the overall structure through vander Waals interactions.

Painting Supramolecular Polymers in Organic Solvents by Super-resolution Microscopy

PubMed Central

2018-01-01

Despite the rapid development of complex functional supramolecular systems, visualization of these architectures under native conditions at high resolution has remained a challenging endeavor. Super-resolution microscopy was recently proposed as an effective tool to unveil one-dimensional nanoscale structures in aqueous media upon chemical functionalization with suitable fluorescent probes. Building upon our previous work, which enabled photoactivation localization microscopy in organic solvents, herein, we present the imaging of one-dimensional supramolecular polymers in their native environment by interface point accumulation for imaging in nanoscale topography (iPAINT). The noncovalent staining, typical of iPAINT, allows the investigation of supramolecular polymers’ structure in situ without any chemical modification. The quasi-permanent adsorption of the dye to the polymer is exploited to identify block-like arrangements within supramolecular fibers, which were obtained upon mixing homopolymers that were prestained with different colors. The staining of the blocks, maintained by the lack of exchange of the dyes, permits the imaging of complex structures for multiple days. This study showcases the potential of PAINT-like strategies such as iPAINT to visualize multicomponent dynamic systems in their native environment with an easy, synthesis-free approach and high spatial resolution. PMID:29697958

Implantable polymer/metal thin film structures for the localized treatment of cancer by Joule heating

NASA Astrophysics Data System (ADS)

Kan-Dapaah, Kwabena; Rahbar, Nima; Theriault, Christian; Soboyejo, Wole

2015-04-01

This paper presents an implantable polymer/metal alloy thin film structure for localized post-operative treatment of breast cancer. A combination of experiments and models is used to study the temperature changes due to Joule heating by patterned metallic thin films embedded in poly-dimethylsiloxane. The heat conduction within the device and the surrounding normal/cancerous breast tissue is modeled with three-dimensional finite element method (FEM). The FEM simulations are used to explore the potential effects of device geometry and Joule heating on the temperature distribution and lesion (thermal dose). The FEM model is validated using a gel model that mimics biological media. The predictions are also compared to prior results from in vitro studies and relevant in vivo studies in the literature. The implications of the results are discussed for the potential application of polymer/metal thin film structures in hyperthermic treatment of cancer.

Probing the effect of polymer molecular weight on penetration into the wood cell wall using polyethylenimine (PEI) as a model compound.

PubMed

Dorvel, Brian; Boopalachandran, Praveenkumar; Chen, Ida; Bowling, Andrew; Williams, Kerry; King, Steve

2018-05-01

Decking is one of the largest applications for the treated wood market. The most challenging property to obtain for treated wood is dimensional stability, which can be achieved, in part, by cell wall bulking, cell wall polymer crosslinking and removal of hygroscopic components in the cell wall. A commonly accepted key requirement is for the actives to infuse through the cell wall, which has a microporosity of ∼5-13 nm. Equally as challenging is being able to measure and quantify the cell wall penetration. Branched polyethylenimine (PEI) was studied as a model polymer for penetration due to its water solubility, polarity, variable molecular weight ranges, and ability to form a chelation complex with preservative metals to treat lumbers. Two different molecular weight polyethylenimines (PEI), one with a weight average molecular weight (Mw) equal to 800 Da and the other 750 000 Da, were investigated for penetration by microscopy and spectroscopy techniques. Analytical methods were developed to both create smooth interfaces and for relative quantitation and visualisation of PEI penetration into the wood. The results showed both PEI with Mw of 800 Da and PEI with Mw of 750 000 Da coated the lumens in high density. However, only the PEI with Mw of 800 appeared to penetrate the cell walls in sufficient levels. Literature has shown the hydrodynamic radii of PEI 750 000 is near 29 nm, whereas a smaller PEI at 25 K showed 4.5 nm. Most importantly the results, based on methods developed, show how molecular weight and tertiary structure of the polymer can affect its penetration, with the microporosity of the wood being the main barrier. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Porous, Hyper-cross-linked, Three-Dimensional Polymer as Stable, High Rate Capability Electrode for Lithium-Ion Battery.

PubMed

Mukherjee, Debdyuti; Gowda Y K, Guruprasada; Makri Nimbegondi Kotresh, Harish; Sampath, S

2017-06-14

Organic materials containing active carbonyl groups have attracted considerable attention as electrodes in Li-ion batteries due to their reversible redox activity, ability to retain capacity, and, in addition, their ecofriendly nature. Introduction of porosity will help accommodate as well as store small ions and molecules reversibly. In the present work, we introduce a mesoporous triptycene-related, rigid network polymer with high specific surface area as an electrode material for rechargeable Li-ion battery. The designed polymer with a three-dimensional (3D), rigid porous network allows free movement of ions/electrolyte as well as helps in interacting with the active anhydride moieties (containing two carbonyl groups). Considerable intake of Li + ions giving rise to very high specific capacity of 1100 mA h g -1 at a discharge current of 50 mA g -1 and ∼120 mA h g -1 at a high discharge current of 3 A g -1 are observed with excellent cyclability up to 1000 cycles. This remarkable rate capability, which is one of the highest among the reported organic porous polymers to date, makes the triptycene-related rigid 3D network a very good choice for Li-ion batteries and opens up a new method to design polymer-based electrode materials for metal-ion battery technology.

COMMUNICATION: Resonant activation in polymer translocation: new insights into the escape dynamics of molecules driven by an oscillating field

NASA Astrophysics Data System (ADS)

Pizzolato, N.; Fiasconaro, A.; Persano Adorno, D.; Spagnolo, B.

2010-09-01

The translocation of molecules across cellular membranes or through synthetic nanopores is strongly affected by thermal fluctuations. In this work we study how the dynamics of a polymer in a noisy environment changes when the translocation process is driven by an oscillating electric field. An improved version of the Rouse model for a flexible polymer has been adopted to mimic the molecular dynamics, by taking into account the harmonic interactions between adjacent monomers and the excluded-volume effect by introducing a Lennard-Jones potential between all beads. A bending recoil torque has also been included in our model. The polymer dynamics is simulated in a two-dimensional domain by numerically solving the Langevin equations of motion. Thermal fluctuations are taken into account by introducing a Gaussian uncorrelated noise. The mean first translocation time of the polymer centre of inertia shows a minimum as a function of the frequency of the oscillating forcing field. This finding represents the first evidence of the resonant activation behaviour in the dynamics of polymer translocation.

Thermoplastic pultrusion development and characterization of residual in pultruded composites with modeling and experiments

NASA Astrophysics Data System (ADS)

Jamiyanaa, Khongor

Pultrusion processing is a technique to make highly aligned fiber reinforced polymer composites. Thermoset pultrusion is a mature process and well established, while thermoplastic pultrusion in still in its infancy. Thermoplastic pultrusion has not been well established because thermoplastic resins are difficult to process due to their high viscosity. However, thermoplastic resins offer distinct advantages that make thermoplastic pultrusion worth exploring. The present work centers on developing a method to design and validate a die for a thermoplastic pultrusion system. Analytical models and various software tools were used to design a pultrusion die. Experimental measurements have been made to validate the models. One-dimensional transient heat transfer analysis was used to calculate the time required for pre-impregnated E-Glass/Polypropylene tapes to melt and consolidate into profiled shapes. Creo Element/Pro 1.0 was used to design the die, while ANSYS Work Bench 14.0 was used to conduct heat transfer analysis to understand the temperature profile of the pultrusion apparatus. Additionally Star-CCM+ was used to create a three-dimensional fluid flow model to capture the molten polymer flow inside the pultrusion die. The fluid model was used to understand the temperature of the flow and the force required to pull the material at any given temperature and line speed. A complete pultrusion apparatus including the die, heating unit, cooling unit, and the frame has been designed and manufactured as guided by the models, and pultruded profiles have been successfully produced. The results show that the analytical model and the fluid model show excellent correlation. The predicted and measured pulling forces are in agreement and show that the pull force increases as the pull speed increases. Furthermore, process induced residual stress and its influence on dimensional instability, such as bending or bowing, on pultruded composites was analyzed. The study indicated that unbalanced layup can produce asymmetrical residual stress through the thickness and causes the part to bow. Furthermore, the residual stress through the thickness was mapped with excellent accuracy. A design of experiments around the processing parameters indicated that increase in pull speed or decrease in die temperature increased the residual stress within the part.

Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Drozdov, A. D.; deClaville Christiansen, J.

2015-07-01

A constitutive model is developed for the elastic response of an anionic polyelectrolyte gel under swelling in water with an arbitrary pH and an arbitrary molar fraction of dissolved monovalent salt. A gel is treated as a three-phase medium consisting of a solid phase (polymer network), solvent (water), and solute (mobile ions). Transport of solvent and solute is thought of as their diffusion through the polymer network accelerated by an electric field formed by mobile and fixed ions and accompanied by chemical reactions (dissociation of functional groups attached to polymer chains and formation of ion pairs between bound charges and mobile counter-ions). Constitutive equations are derived by means of the free energy imbalance inequality for an arbitrary three-dimensional deformation with finite strains. These relations are applied to analyze equilibrium swelling diagrams on poly(acrylic acid) gel, poly(methacrylic acid) gel, and three composite hydrogels under water uptake in a bath (i) with a fixed molar fraction of salt and varied pH, and (ii) with a fixed pH and varied molar fraction of salt. To validate the ability of the model to predict observations quantitatively, material constants are found by matching swelling curves under one type of experimental conditions and results of simulation are compared with experimental data in the other type of tests.

Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

NASA Astrophysics Data System (ADS)

Luo, Qianqian; Han, Ying; Lin, Hechun; Zhang, Yuanyuan; Duan, Chungang; Peng, Hui

2017-03-01

One dimensional coordination polymer Gd[(SO4)(NO3)(C2H6SO)2] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO42- ions to generate a 1-D chain, and all oxygen atoms in SO42- groups are connected to three nearest Gd atoms in μ3:η1:η1:η2 fashion. Gd, S and N from SO42- and NO3- are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with -ΔSm=28.8 J Kg-1 K-1 for ΔH=7 T.

Bridging the Resolution Gap in Structural Modeling of 3D Genome Organization

PubMed Central

Marti-Renom, Marc A.; Mirny, Leonid A.

2011-01-01

Over the last decade, and especially after the advent of fluorescent in situ hybridization imaging and chromosome conformation capture methods, the availability of experimental data on genome three-dimensional organization has dramatically increased. We now have access to unprecedented details of how genomes organize within the interphase nucleus. Development of new computational approaches to leverage this data has already resulted in the first three-dimensional structures of genomic domains and genomes. Such approaches expand our knowledge of the chromatin folding principles, which has been classically studied using polymer physics and molecular simulations. Our outlook describes computational approaches for integrating experimental data with polymer physics, thereby bridging the resolution gap for structural determination of genomes and genomic domains. PMID:21779160

Simple triple-state polymer actuators with controllable folding characteristics

NASA Astrophysics Data System (ADS)

Chen, Shuyang; Li, Jing; Fang, Lichen; Zhu, Zeyu; Kang, Sung Hoon

2017-03-01

Driven by the interests in self-folding, there have been studies developing artificial self-folding structures at different length scales based on various polymer actuators that can realize dual-state actuation. However, their unidirectional nature limits the applicability of the actuators for a wide range of multi-state self-folding behaviors. In addition, complex fabrication and programming procedures hinder broad applications of existing polymer actuators. Moreover, few of the existing polymer actuators are able to show the self-folding behaviors with the precise control of curvature and force. To address these issues, we report an easy-to-fabricate triple-state actuator with controllable folding behaviors based on bilayer polymer composites with different glass transition temperatures. Initially, the fabricated actuator is in the flat state, and it can sequentially self-fold to angled folding states of opposite directions as it is heated up. Based on an analytical model and measured partial recovery behaviors of polymers, we can accurately control the folding characteristics (curvature and force) for the rational design. To demonstrate an application of our triple-state actuator, we have developed a self-folding transformer robot which self-folds from a two-dimensional sheet into a three-dimensional boat-like configuration and transforms from the boat shape to a car shape with the increase in the temperature applied to the actuator. Our findings offer a simple approach to generate multiple configurations from a single system by harnessing behaviors of polymers with the rational design.

Fast Assembly of Gold Nanoparticles in Large-Area 2D Nanogrids Using a One-Step, Near-Infrared Radiation-Assisted Evaporation Process.

PubMed

Utgenannt, André; Maspero, Ross; Fortini, Andrea; Turner, Rebecca; Florescu, Marian; Jeynes, Christopher; Kanaras, Antonios G; Muskens, Otto L; Sear, Richard P; Keddie, Joseph L

2016-02-23

When fabricating photonic crystals from suspensions in volatile liquids using the horizontal deposition method, the conventional approach is to evaporate slowly to increase the time for particles to settle in an ordered, periodic close-packed structure. Here, we show that the greatest ordering of 10 nm aqueous gold nanoparticles (AuNPs) in a template of larger spherical polymer particles (mean diameter of 338 nm) is achieved with very fast water evaporation rates obtained with near-infrared radiative heating. Fabrication of arrays over areas of a few cm(2) takes only 7 min. The assembly process requires that the evaporation rate is fast relative to the particles' Brownian diffusion. Then a two-dimensional colloidal crystal forms at the falling surface, which acts as a sieve through which the AuNPs pass, according to our Langevin dynamics computer simulations. With sufficiently fast evaporation rates, we create a hybrid structure consisting of a two-dimensional AuNP nanoarray (or "nanogrid") on top of a three-dimensional polymer opal. The process is simple, fast, and one-step. The interplay between the optical response of the plasmonic Au nanoarray and the microstructuring of the photonic opal results in unusual optical spectra with two extinction peaks, which are analyzed via finite-difference time-domain method simulations. Comparison between experimental and modeling results reveals a strong interplay of plasmonic modes and collective photonic effects, including the formation of a high-order stopband and slow-light-enhanced plasmonic absorption. The structures, and hence their optical signatures, are tuned by adjusting the evaporation rate via the infrared power density.

Order and Disorder in Short Block Polymers

NASA Astrophysics Data System (ADS)

Bates, Frank S.

2015-03-01

Block polymers have captivated the interest of scientists and engineers for more than half a century. The phase behavior of this class of self-assembling soft material is well understood in the limit of infinite molecular weight, based on the self-consistent mean-field theory pioneered by Leibler. At practical molecular sizes, typically around N ~ 1000 repeat units, fluctuation effects become highly significant in the vicinity of the order disorder transition. One-loop corrections to mean-field theory, first described by Brazovski and applied to block polymers by Fredrickson and Helfand, are not expected to be applicable in this limit. Moreover, the drive towards ever smaller domain dimensions, and the opportunity to circumvent transport limitations associated with entanglements, have motivated experiments with yet lower molecular weight block polymers, N less than 100. This presentation will describe the consequences of fluctuations and the equilibrium structural properties of short model AB diblock polymers in the symmetric (f = 1/2) and asymmetric (f --> 0) regimes above and below the order-disorder transition. The consequences of fluctuations and access to equilibrium states will be described in the 1-dimensional stripped (lamellar) phase and the ordering of point particles in 3-dimensions, respectively. As N --> 1 computer simulation with realistic molecular detail becomes feasible presenting exciting opportunities to compliment the associated theoretical challenges. Research in collaboration with Sangwoo Lee, Chris Leighton and Timothy Gillard and Supported by NSF-DMR-1104368.

Assessment of femtosecond laser induced periodic surface structures on polymer films.

PubMed

Rebollar, Esther; Vázquez de Aldana, Javier R; Martín-Fabiani, Ignacio; Hernández, Margarita; Rueda, Daniel R; Ezquerra, Tiberio A; Domingo, Concepción; Moreno, Pablo; Castillejo, Marta

2013-07-21

In this work we present the formation of laser induced periodic surface structures (LIPSS) on spin-coated thin films of several model aromatic polymers including poly(ethylene terephthalate), poly(trimethylene terephthalate) and poly carbonate bis-phenol A upon irradiation with femtosecond pulses of 795 and 265 nm at fluences well below the ablation threshold. LIPSS are formed with period lengths similar to the laser wavelength and parallel to the direction of the laser polarization vector. Formation of LIPSS upon IR irradiation at 795 nm, a wavelength at which the polymers absorb weakly, contrasts with the absence of LIPSS in this spectral range upon irradiation with nanosecond pulses. Real and reciprocal space characterization of LIPSS obtained by Atomic Force Microscopy (AFM) and Grazing Incidence Small Angle X-ray Scattering (GISAXS), respectively, yields well correlated morphological information. Comparison of experimental and simulated GISAXS patterns suggests that LIPSS can be suitably described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice. Fluorescence measurements, after laser irradiation, provide indirect information about dynamics and structure of the polymer at the molecular level. Our results indicate that the LIPSS are formed by interference of the incident and surface scattered waves. As a result of this process, heating of the polymer surface above its glass transition temperature takes place enabling LIPSS formation.

Crystal structure of catena-poly[[aquadi-n-propyl­tin(IV)]-μ-oxalato

PubMed Central

Reichelt, Martin; Reuter, Hans

2014-01-01

The title compound, [Sn(C3H7)2(H2O)(C2O4)]n, represents the first diorganotin(IV) oxalate hydrate to be structurally characterized. The tin(IV) atom of the one-dimensional coordination polymer is located on a twofold rotation axis and is coordinated by two chelating oxalate ligands with two slightly different Sn—O bond lengths of 2.290 (2) and 2.365 (2) Å, two symmetry-related n-propyl groups with a Sn—C bond lengths of 2.127 (3) Å, and a water mol­ecule with a Sn—O bond length of 2.262 (2) Å. The coordination polyhedron around the SnIV atom is a slightly distorted penta­gonal bipyramid with a nearly linear axis between the trans-oriented n-propyl groups [C—Sn—C = 176.8 (1)°]. The bond angles between the oxygen atoms of the equatorial plane range from 70.48 (6)° to 76.12 (8)°. A one-dimensional coordination polymer results from the less asymmetric bilateral coordination of the centrosymmetric oxalate anion, inter­nally reflected by two slightly different C—O bond lengths of 1.248 (3) and 1.254 (3) Å. The chains of the polymer propagate parallel to [001] and are held together by hydrogen bonds between water mol­ecules and oxalate anions of neighboring chains, leading to a two-dimensional network parallel to (100). PMID:25249862

Three-dimensionally modulated anisotropic structure for diffractive optical elements created by one-step three-beam polarization holographic photoalignment

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

Kawai, Kotaro, E-mail: s135016@stn.nagaokaut.ac.jp; Sakamoto, Moritsugu; Noda, Kohei

2016-03-28

A diffractive optical element with a three-dimensional liquid crystal (LC) alignment structure for advanced control of polarized beams was fabricated by a highly efficient one-step photoalignment method. This study is of great significance because different two-dimensional continuous and complex alignment patterns can be produced on two alignment films by simultaneously irradiating an empty glass cell composed of two unaligned photocrosslinkable polymer LC films with three-beam polarized interference beam. The polarization azimuth, ellipticity, and rotation direction of the diffracted beams from the resultant LC grating widely varied depending on the two-dimensional diffracted position and the polarization states of the incident beams.more » These polarization diffraction properties are well explained by theoretical analysis based on Jones calculus.« less

Surface Enhanced Raman Scattering Monitoring of Chain Alignment in Freely Suspended Nanomembranes

NASA Astrophysics Data System (ADS)

Jiang, Chaoyang; Lio, Wilber Y.; Tsukruk, Vladimir V.

2005-09-01

The molecular chain reorganization in freely standing membranes with encapsulated gold nanoparticles was studied with surface enhanced Raman scattering (SERS) in the course of their elastic deformations. The efficient SERS was enabled by optimizing the design of gold nanoparticle forming chainlike aggregates, thus creating an exceptional ability to conduct in situ monitoring. Small deformations resulted in the radial orientation of side phenyl rings of polymer backbones while larger deflections led to the polymer chains bridging adjacent nanoparticles within one-dimensional aggregates.

Obtaining short-fiber orientation model parameters using non-lubricated squeeze flow

NASA Astrophysics Data System (ADS)

Lambert, Gregory; Wapperom, Peter; Baird, Donald

2017-12-01

Accurate models of fiber orientation dynamics during the processing of polymer-fiber composites are needed for the design work behind important automobile parts. All of the existing models utilize empirical parameters, but a standard method for obtaining them independent of processing does not exist. This study considers non-lubricated squeeze flow through a rectangular channel as a solution. A two-dimensional finite element method simulation of the kinematics and fiber orientation evolution along the centerline of a sample is developed as a first step toward a fully three-dimensional simulation. The model is used to fit to orientation data in a short-fiber-reinforced polymer composite after squeezing. Fiber orientation model parameters obtained in this study do not agree well with those obtained for the same material during startup of simple shear. This is attributed to the vastly different rates at which fibers orient during shearing and extensional flows. A stress model is also used to try to fit to experimental closure force data. Although the model can be tuned to the correct magnitude of the closure force, it does not fully recreate the transient behavior, which is attributed to the lack of any consideration for fiber-fiber interactions.

Simplified charge separation energetics in a two-dimensional model for polymer-based photovoltaic cells.

PubMed

Sylvester-Hvid, Kristian O; Ratner, Mark A

2005-01-13

An extension of our two-dimensional working model for photovoltaic behavior in binary polymer and/or molecular photoactive blends is presented. The objective is to provide a more-realistic description of the charge generation and charge separation processes in the blend system. This is achieved by assigning an energy to each of the possible occupation states, describing the system according to a simple energy model for exciton and geminate electron-hole pair configurations. The energy model takes as primary input the ionization potential, electron affinity and optical gap of the components of the blend. The underlying photovoltaic model considers a nanoscopic subvolume of a photoactive blend and represents its p- and n-type domain morphology, in terms of a two-dimensional network of donor and acceptor sites. The nearest-neighbor hopping of charge carriers in the illuminated system is described in terms of transitions between different occupation states. The equations governing the dynamics of these states are cast into a linear master equation, which can be solved for arbitrary two-dimensional donor-acceptor networks, assuming stationary conditions. The implications of incorporating the energy model into the photovoltaic model are illustrated by simulations of the short circuit current versus thickness of the photoactive blend layer for different choices of energy parameters and donor-acceptor topology. The results suggest the existence of an optimal thickness of the photoactive film in bulk heterojunctions, based on kinetic considerations alone, and that this optimal thickness is very sensitive to the choice of energy parameters. The results also indicate space-charge limiting effects for interpenetrating donor-acceptor networks with characteristic domain sizes in the nanometer range and high driving force for the photoinduced electron transfer across the donor-acceptor internal interface.

Nanocarbon/elastomer composites: Characterization and applications in photo-mechanical actuation

NASA Astrophysics Data System (ADS)

Loomis, Robert James, III

The magnitude and direction of photo-mechanical actuation responses generated in carbon nanostructure/elastomer composites depend on applied pre-strains. At low levels of pre-strains (3--9%), actuators show reversible photo-induced expansion while at high levels (15--40%), actuators exhibit reversible contraction. Large, light-induced reversible and elastic responses of graphene nanoplatelet (GNP) polymer composites were demonstrated for the first time, with an extraordinary optical-to-mechanical energy conversion factor (etaM) of 7--9 MPa/W. Following this demonstration, similar elastomeric composite were fabricated with a variety of carbon nanostructures. Investigation into photo-actuation properties of these composites revealed both layer-dependent, as well as dimensionally-dependent responses. For a given carbon concentration, both steady-state photo-mechanical stress response and energy conversion efficiency were found to be directly related to dimensional state of carbon nanostructure additive, with one-dimensional (1D) carbon nanotubes demonstrating the highest responses (˜60 kPa stress and ˜5 x 10-3% efficiency at just 1 wt% loading) and three-dimensional (3D) highly ordered pyrolytic graphite demonstrating the lowest responses. Furthermore, development of an advanced dispersion technique (evaporative mixing) resulted in the ability to fabricate conductive composites. Actuation and relaxation kinetics responses were investigated and found to be related not to dimensionality, but rather the percolation threshold of carbon nanostructure additive in the polymer. Establishing a connective network of carbon nanostructure additive allowed for energy transduction responsible for photo-mechanical effect to activate carbon beyond the infrared (IR) illumination point, resulting in enhanced actuation. Additionally, in the conductive samples photo-conductivity as a function of applied pre-strain was also measured. Photo-conductive response was found to be inversely proportional to applied pre-strain, demonstrating mechanical coupling. Following investigation into photo-mechanical actuation responses between the various carbon forms, use of these composite actuators to achieve both macroscopic as well as microscopic movement in practical applications was evaluated. Using dual GNP/elastomer actuators, a two-axis sub-micron translation stage was developed, and allowed for two-axis photo-thermal positioning (˜100 microm per axis) with 120 nm resolution (limitation of the feedback sensor) and ˜5 microm/s actuation speeds. A proportional-integral-derivative control loop automatically stabilizes the stage against thermal drift, as well as random thermal-induced position fluctuations (up to the bandwidth of the feedback and position sensor). Nanopositioner performance characteristics were found to be on par with other commercial systems, with resolution limited only by the feedback system used. A mathematical model was developed to describe the elastomeric composite actuators as a series of n springs, with each spring element having its own independent IR-tunable spring constant. Effects of illumination intensity, position, and amount of the composite actuator illuminated are discussed. This model provided several additional insights, such as demonstrating the ability to place not just one, but multiple stages on a single polymer composite strip and position them independently from one another, a benefit not seen in any other type of positioning system. Further investigation yielded interesting and novel photo-mechanical properties with actuation visible on macroscopic scales. Addition of a third component (thermally expanding microspheres), produced a new class of stimuli-responsive expanding polymer composites with ability to unidirectionally transform physical dimensions, elastic modulus, density, and electrical resistance. Carbon nanotubes and core-shell acrylic microspheres were dispersed in polydimethylsiloxane, resulting in composites that exhibit a binary set of material properties. Upon thermal or IR stimuli, liquid cores encapsulated within the microspheres vaporize, expanding the surrounding shells and stretching the matrix. Microsphere expansion results in visible dimensional changes, regions of reduced polymeric chain mobility, nanotube tensioning, and overall elastic to plastic-like transformation of the composite. Transformations include macroscopic volume expansion (>500%), density reduction (>80%), and elastic modulus increase (>675%). Additionally, conductive nanotubes allow for remote expansion monitoring and exhibit distinct loading-dependent electrical responses. (Abstract shortened by UMI.).

Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

NASA Astrophysics Data System (ADS)

Archer, Lynden

Addition of nanoparticles to polymers is a well-practiced methodology for augmenting various properties of the polymer host, including mechanical strength, thermal stability, barrier properties, dimensional stability and wear resistance. Many of these property changes are known to arise from nanoparticle-induced modification of polymer structure and chain dynamics, which are strong functions of the dispersion state of the nanoparticles' and on their relative size (D) to polymer chain dimensions (e.g. Random coil radius Rg or entanglement mesh size a) . This talk will discuss polymer nanocomposites (PNCs) comprised of Polyethylene Glycol (PEG) tethered silica nanoparticles (SiO2-PEG) dispersed in polymers as model systems for investigating phase stability and dynamics of PNCs. On the basis of small-angle X-ray Scattering, it will be shown that favorable enthalpic interactions between particle-tethered chains and a polymer host provides an important mechanism for creating PNCs in which particle aggregation is avoided. The talk will report on polymer and particle scale dynamics in these materials and will show that grafted nanoparticles well dispersed in a polymer host strongly influence the host polymer relaxation dynamics on all timescales and the polymers in turn produce dramatic changes in the nature (from diffusive to hyperdiffusive) and speed of nano particle decorrelation dynamics at the polymer entanglement threshold. A local viscosity model capable of explaining these observations is discussed and the results compared with scaling theories for NP motions in polymers This material is based on work supported by the National Science Foundation Award Nos. DMR-1609125 and CBET-1512297.

Nanometer-sized materials for solid-phase extraction of trace elements.

PubMed

Hu, Bin; He, Man; Chen, Beibei

2015-04-01

This review presents a comprehensive update on the state-of-the-art of nanometer-sized materials in solid-phase extraction (SPE) of trace elements followed by atomic-spectrometry detection. Zero-dimensional nanomaterials (fullerene), one-dimensional nanomaterials (carbon nanotubes, inorganic nanotubes, and nanowires), two-dimensional nanomaterials (nanofibers), and three-dimensional nanomaterials (nanoparticles, mesoporous nanoparticles, magnetic nanoparticles, and dendrimers) for SPE are discussed, with their application for trace-element analysis and their speciation in different matrices. A variety of other novel SPE sorbents, including restricted-access sorbents, ion-imprinted polymers, and metal-organic frameworks, are also discussed, although their applications in trace-element analysis are relatively scarce so far.

Dynamic Self-Assembly of Gold/Polymer Nanocomposites: pH-Encoded Switching between 1D Nanowires and 3D Nanosponges.

PubMed

Zhang, Qi; Xu, Tian-Yi; Zhao, Cai-Xin; Jin, Wei-Hang; Wang, Qian; Qu, Da-Hui

2017-10-05

The design of tunable dynamic self-assembly of nanoparticles with switchable assembled dimensions and morphologies is a challenging goal whose realization is vital for the evolution of smart nanomaterials. Herein, we report on chitosan polymer as an effective supramolecular "glue" for aldehyde-modified Au nanoparticles to reversibly modulate the states of self-assembled nanocomposites. By simultaneous integration of dynamic covalent Schiff base interactions and noncovalent hydrogen bonds, the chitosan/Au nanocomposites could reversibly transform their assembled morphologies from one-dimensional nanowires to three-dimensional nanosponges in response to the variation of pH value. Moreover, the obtained nanosponges could be used as an efficient pH-controlled cargo release system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical Properties of Polymer Nano-composites

NASA Astrophysics Data System (ADS)

Srivastava, Iti

Thermoset polymer composites are increasingly important in high-performance engineering industries due to their light-weight and high specific strength, finding cutting-edge applications such as aircraft fuselage material and automobile parts. Epoxy is the most widely employed thermoset polymer, but is brittle due to extensive cross-linking and notch sensitivity, necessitating mechanical property studies especially fracture toughness and fatigue resistance, to ameliorate the low crack resistance. Towards this end, various nano and micro fillers have been used with epoxy to form composite materials. Particularly for nano-fillers, the 1-100 nm scale dimensions lead to fascinating mechanical properties, oftentimes proving superior to the epoxy matrix. The chemical nature, topology, mechanical properties and geometry of the nano-fillers have a profound influence on nano-composite behavior and hence are studied in the context of enhancing properties and understanding reinforcement mechanisms in polymer matrix nano-composites. Using carbon nanotubes (CNTs) as polymer filler, uniquely results in both increased stiffness as well as toughness, leading to extensive research on their applications. Though CNTs-polymer nano-composites offer better mechanical properties, at high stress amplitude their fatigue resistance is lost. In this work covalent functionalization of CNTs has been found to have a profound impact on mechanical properties of the CNT-epoxy nano-composite. Amine treated CNTs were found to give rise to effective fatigue resistance throughout the whole range of stress intensity factor, in addition to significantly enhancing fracture toughness, ductility, Young's modulus and average hardness of the nano-composite by factors of 57%, 60%, 30% and 45% respectively over the matrix as a result of diminished localized cross-linking. Graphene, a one-atom-thick sheet of atoms is a carbon allotrope, which has garnered significant attention of the scientific community and is predicted to out-perform nanotubes. In the last few years, work has been done by researchers to study bulk mechanical properties of graphene platelets in polymer matrix. This thesis reports the extensive improvements observed in fatigue resistance and fracture toughness of epoxy using graphene platelet as a filler in very small quantities. Though significant property improvements like 75% increase in fracture toughness and 25-fold increase in fatigue resistance were observed for graphene epoxy nano-composites, the toughening mechanisms could not be delineated without thermo-mechanical and micro-mechanical tests. In this work, the bulk mechanical properties of graphene platelet-polymer nano-composites are studied and presented and the toughness mechanisms are identified by fractography, differential scanning calorimetry, and Raman spectroscopy; and then compared to predictions by theoretical models. Strong adherence to the matrix was found to be the key mechanism responsible for the effective reinforcement provided by graphene to the polymer. The strong graphene platelet-matrix interface also leads to extensive crack deflection, which was observed to be the major toughening mechanism in the nano-composite. In this thesis, the bulk mechanical property results are complemented by in-depth characterization of filler-polymer interfacial interactions and interphase formation using a battery of techniques including Raman spectroscopy and atomic force microscopy. Theoretical and empirical models proposed by Faber & Evans and Pezzotti were critically studied and applied. Pezzotti's model was found to corroborate well with experimental results and provided insight into enhancement mechanisms and explains the mechanisms underpinning the toughness loss at high graphene platelet weight fraction. The thesis provides conclusive evidences for the superiority of graphene as a filler for reinforcing polymer matrices. In conclusion, the thesis presents a thorough investigation of one- and two-dimensional carbon nanomaterials as fillers for high-performance polymer nano-composites. The extensive studies performed on graphene provide a strong foundation for graphene as a potential candidate for reinforcing polymers. The superior performance of graphene as a filler is attributed to graphene's high specific surface area, two-dimensional sheet geometry, strong filler-matrix adhesion and the outstanding mechanical properties of the sp2 carbon-bonding network in graphene. The improved mechanical properties of the graphene-polymer nano-composites, concurrent with the cost-effective production are both vital requirements of the industry in adoption of high strength-to-weight ratio polymer composites for various structural applications.

A two-dimensional ZnII coordination polymer constructed from benzene-1,2,3-tricarboxylic acid and N,N'-bis[(pyridin-4-yl)methylidene]hydrazine.

PubMed

Wang, Xiangfei; Yang, Fang; Tang, Meng; Yuan, Limin; Liu, Wenlong

2015-07-01

The hydrothermal synthesis of the novel complex poly[aqua(μ4-benzene-1,2,3-tricarboxylato)[μ2-4,4'-(hydrazine-1,2-diylidenedimethanylylidene)dipyridine](μ3-hydroxido)dizinc(II)], [Zn(C9H3O6)(OH)(C12H10N4)(H2O)]n, is described. The benzene-1,2,3-tricarboxylate ligand connects neighbouring Zn4(OH)2 secondary building units (SBUs) producing an infinite one-dimensional chain. Adjacent one-dimensional chains are connected by the N,N'-bis[(pyridin-4-yl)methylidene]hydrazine ligand, forming a two-dimensional layered structure. Adjacent layers are stacked to generate a three-dimensional supramolecular architecture via O-H...O hydrogen-bond interactions. The thermal stability of this complex is described and the complex also appears to have potential for application as a luminescent material.

Thermal modelling of Li-ion polymer battery for electric vehicle drive cycles

NASA Astrophysics Data System (ADS)

Chacko, Salvio; Chung, Yongmann M.

2012-09-01

Time-dependent, thermal behaviour of a lithium-ion (Li-ion) polymer cell has been modelled for electric vehicle (EV) drive cycles with a view to developing an effective battery thermal management system. The fully coupled, three-dimensional transient electro-thermal model has been implemented based on a finite volume method. To support the numerical study, a high energy density Li-ion polymer pouch cell was tested in a climatic chamber for electric load cycles consisting of various charge and discharge rates, and a good agreement was found between the model predictions and the experimental data. The cell-level thermal behaviour under stressful conditions such as high power draw and high ambient temperature was predicted with the model. A significant temperature increase was observed in the stressful condition, corresponding to a repeated acceleration and deceleration, indicating that an effective battery thermal management system would be required to maintain the optimal cell performance and also to achieve a full battery lifesapn.

Characterization of Hydrophobic Interactions of Polymers with Water and Phospholipid Membranes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Drenscko, Mihaela

Polymers and lipid membranes are both essential soft materials. The structure and hydrophobicity/hydrophilicity of polymers, as well as the solvent they are embedded in, ultimately determines their size and shape. Understating the variation of shape of the polymer as well as its interactions with model biological membranes can assist in understanding the biocompatibility of the polymer itself. Computer simulations, in particular molecular dynamics, can aid in characterization of the interaction of polymers with solvent, as well as polymers with model membranes. In this thesis, molecular dynamics serve to describe polymer interactions with a solvent (water) and with a lipid membrane. To begin with, we characterize the hydrophobic collapse of single polystyrene chains in water using molecular dynamics simulations. Specifically, we calculate the potential of mean force for the collapse of a single polystyrene chain in water using metadynamics, comparing the results between all atomistic with coarse-grained molecular simulation. We next explore the scaling behavior of the collapsed globular shape at the minimum energy configuration, characterized by the radius of gyration, as a function of chain length. The exponent is close to one third, consistent with that predicted for a polymer chain in bad solvent. We also explore the scaling behavior of the Solvent Accessible Surface Area (SASA) as a function of chain length, finding a similar exponent for both all-atomistic and coarse-grained simulations. Furthermore, calculation of the local water density as a function of chain length near the minimum energy configuration suggests that intermediate chain lengths are more likely to form dewetted states, as compared to shorter or longer chain lengths. Next, in order to investigate the molecular interactions between single hydrophobic polymer chains and lipids in biological membranes and at lipid membrane/solvent interface, we perform a series of molecular dynamics simulations of small membranes using all atomistic and coarse-grained methods. The molecular interaction between common polymer chains used in biomedical applications and the cell membrane is unknown. This interaction may affect the biocompatibility of the polymer chains. Molecular dynamics simulations offer an emerging tool to characterize the interaction between common degradable polymer chains used in biomedical applications, such as polycaprolactone, and model cell membranes. We systematically characterize with long-time all-atomistic molecular dynamics simulations the interaction between single polycaprolactone chains of varying chain lengths with a model phospholipid membrane. We find that the length of polymer chain greatly affects the nature of interaction with the membrane, as well as the membrane properties. Furthermore, we next utilize advanced sampling techniques in molecular dynamics to characterize the two-dimensional free energy surface for the interaction of varying polymer chain lengths (short, intermediate, and long) with model cell membranes. We find that the free energy minimum shifts from the membrane-water interface to the hydrophobic core of the phospholipid membrane as a function of chain length. These results can be used to design polymer chain lengths and chemistries to optimize their interaction with cell membranes at the molecular level.

Doubly self-consistent field theory of grafted polymers under simple shear in steady state.

PubMed

Suo, Tongchuan; Whitmore, Mark D

2014-03-21

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkman equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.

Measurement of in-plane thermal conductivity in polymer films

NASA Astrophysics Data System (ADS)

Wei, Qingshuo; Uehara, Chinatsu; Mukaida, Masakazu; Kirihara, Kazuhiro; Ishida, Takao

2016-04-01

Measuring the in-plane thermal conductivity of organic thermoelectric materials is challenging but is critically important. Here, a method to study the in-plane thermal conductivity of free-standing films (via the use of commercial equipment) based on temperature wave analysis is explored in depth. This subject method required a free-standing thin film with a thickness larger than 10 μm and an area larger than 1 cm2, which are not difficult to obtain for most solution-processable organic thermoelectric materials. We evaluated thermal conductivities and anisotropic ratios for various types of samples including insulating polymers, undoped semiconducting polymers, doped conducting polymers, and one-dimensional carbon fiber bulky papers. This approach facilitated a rapid screening of in-plane thermal conductivities for various organic thermoelectric materials.

A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

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

Wang, Jin-Hua; Tang, Gui-Mei, E-mail: meiguit@163.com; Qin, Ting-Xiao

2014-11-15

Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11more » nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one-dimensional structures have been observed. • The properties of second harmonic generation and ferroelectricity for complex 2.« less

Modelling Polymer Deformation and Welding Behaviour during 3D Printing

NASA Astrophysics Data System (ADS)

McIlroy, Claire; Olmsted, Peter

2016-11-01

3D printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The most common method, fused deposition modelling, involves melting a thermoplastic, followed by layer-by-layer extrusion of the material to fabricate a three-dimensional object. The key to the ensuring strength at the weld between these layers is successful inter-diffusion. However, as the printed layer cools towards the glass transition temperature, the time available for diffusion is limited. In addition, the extrusion process significantly deforms the polymer micro-structure prior to welding and consequently affects how the polymers "re-entangle" across the weld. We have developed a simple model of the non-isothermal printing process to explore the effects that typical printing conditions and amorphous polymer rheology have on the ultimate weld structure. In particular, we incorporate both the stretch and orientation of the polymer using the Rolie-Poly constitutive equation to examine how the melt flows through the nozzle and is deposited onto the build plate. We then address how this deformation relaxes and contributes to the thickness and structure of the weld. National Institute for Standards and Technology (NIST) and Georgetown University.

Modelling Polymer Deformation during 3D Printing

NASA Astrophysics Data System (ADS)

McIlroy, Claire; Olmsted, Peter

Three-dimensional printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The fused deposition modelling technique involves melting a thermoplastic, followed by layer-by-layer extrusion to fabricate an object. The key to ensuring strength at the weld between layers is successful inter-diffusion. However, prior to welding, both the extrusion process and the cooling temperature profile can significantly deform the polymer micro-structure and, consequently, how well the polymers are able to ``re-entangle'' across the weld. In particular, polymer alignment in the flow can cause de-bonding of the layers and create defects. We have developed a simple model of the non-isothermal extrusion process to explore the effects that typical printing conditions and material rheology have on the conformation of a polymer melt. In particular, we incorporate both stretch and orientation using the Rolie-Poly constitutive equation to examine the melt structure as it flows through the nozzle, the subsequent alignment with the build plate and the resulting deformation due to the fixed nozzle height, which is typically less than the nozzle radius.

Exciton size and binding energy limitations in one-dimensional organic materials.

PubMed

Kraner, S; Scholz, R; Plasser, F; Koerner, C; Leo, K

2015-12-28

In current organic photovoltaic devices, the loss in energy caused by the charge transfer step necessary for exciton dissociation leads to a low open circuit voltage, being one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy to a value of the order of thermal energy, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley-Queisser limit. We determine the size of the excitons for different organic molecules and polymers by time dependent density functional theory calculations. For optically relevant transitions, the exciton size saturates around 0.7 nm for one-dimensional molecules with a size longer than about 4 nm. For the ladder-type polymer poly(benzimidazobenzophenanthroline), we obtain an exciton binding energy of about 0.3 eV, serving as a lower limit of the exciton binding energy for the organic materials investigated. Furthermore, we show that charge transfer transitions increase the exciton size and thus identify possible routes towards a further decrease of the exciton binding energy.

Photoluminescent lead(II) coordination polymers stabilised by bifunctional organoarsonate ligands

NASA Astrophysics Data System (ADS)

Lin, Jian-Di; Onet, Camelia I.; Schmitt, Wolfgang

2015-04-01

Four lead(II) coordination polymers were isolated under hydro(solvo)thermal conditions. The applied synthetic methodology takes advantage of the coordination behaviour of a new bifunctional organoarsonate ligand, 4-(1, 2, 4-triazol-4-yl)phenylarsonic acid (H2TPAA) and involves the variation of lead(II) reactants, metal/ligand mole ratios, and solvents. The constitutional composition of the four lead(II) coordination polymers can be formulated as [Pb2(TPAA)(HTPAA)(NO3)]·6H2O (1), [Pb2(TPAA)(HTPAA)2]·DMF·0.5H2O (DMF = N, N-Dimethylformamide) (2), [Pb2Cl2(TPAA)H2O] (3), and [Pb3Cl(TPAA)(HTPAA)2H2O]Cl (4). The compounds were characterized by single-crystal and powder x-ray diffraction techniques, thermogravimetric analyses, infra-red spectroscopy, and elemental analyses. Single-crystal x-ray diffraction reveals that 1 and 2 represent two-dimensional (2D) layered structures whilst 3 and 4 form three-dimensional (3D) frameworks. The structures of 1, 2, and 4 contain one-dimensional (1D) {PbII/AsO3} substructures, while 3 is composed of 2D {PbII/AsO3} arrays. Besides their interesting topologies, 1-4 all exhibit photoluminescence properties in the solid state at room temperature.

Polyacrylic acid polymer brushes as substrates for the incorporation of anthraquinone derivatives. Unprecedented application of decorated polymer brushes on organocatalysis

NASA Astrophysics Data System (ADS)

Ruiz-Muelle, Ana Belén; Contreras-Cáceres, Rafael; Oña-Burgos, Pascual; Rodríguez-Dieguez, Antonio; López-Romero, Juan Manuel; Fernández, Ignacio

2018-01-01

The synthesis of amino-terminated anthraquinone derivatives and their incorporation onto polymer brushes for the fabrication of silicon-based nanometric functional coatings are described for the first time. The general process involves the covalent grafting of anthraquinone 1 onto two different polymer-brushes by amidation reactions. They are composed by amino- and carboxy-terminated poly(acrylic acid) chains (PAA-NH2- and PAA-COOH, respectively) tethered by one end to an underlying silicon oxide (SiO2) substrate in a polymer brush configuration. A third substrate is fabricated by UV induced hydrosilylation reaction using undecenoic acid as adsorbate on hydrogen-terminated Si(111) surfaces. One- and two-dimensional nuclear magnetic resonance (NMR), FT-IR, MS and X-ray diffraction (XRD) were used to characterize anthraquinone 1. Ellipsometric and X-ray photoelectron spectroscopy (XPS) measurements demonstrated the presence of the polymer brushes on the silicon wafers, and atomic force microscopy (AFM) was used to study its surface morphology. The covalent linkage between anthraquinone and polymer brushes was proven by XPS and confocal fluorescence microscopy. The resulting surfaces were assayed in the heterogenous organocatalytic transformation of (1H)-indole into 3-benzyl indole with moderate yields but with high recyclability.

Laser-induced porous graphene films from commercial polymers

NASA Astrophysics Data System (ADS)

Lin, Jian; Peng, Zhiwei; Liu, Yuanyue; Ruiz-Zepeda, Francisco; Ye, Ruquan; Samuel, Errol L. G.; Yacaman, Miguel Jose; Yakobson, Boris I.; Tour, James M.

2014-12-01

The cost effective synthesis and patterning of carbon nanomaterials is a challenge in electronic and energy storage devices. Here we report a one-step, scalable approach for producing and patterning porous graphene films with three-dimensional networks from commercial polymer films using a CO2 infrared laser. The sp3-carbon atoms are photothermally converted to sp2-carbon atoms by pulsed laser irradiation. The resulting laser-induced graphene (LIG) exhibits high electrical conductivity. The LIG can be readily patterned to interdigitated electrodes for in-plane microsupercapacitors with specific capacitances of >4 mF cm-2 and power densities of ~9 mW cm-2. Theoretical calculations partially suggest that enhanced capacitance may result from LIG’s unusual ultra-polycrystalline lattice of pentagon-heptagon structures. Combined with the advantage of one-step processing of LIG in air from commercial polymer sheets, which would allow the employment of a roll-to-roll manufacturing process, this technique provides a rapid route to polymer-written electronic and energy storage devices.

Laser-induced porous graphene films from commercial polymers

PubMed Central

Lin, Jian; Peng, Zhiwei; Liu, Yuanyue; Ruiz-Zepeda, Francisco; Ye, Ruquan; Samuel, Errol L. G.; Yacaman, Miguel Jose; Yakobson, Boris I.; Tour, James M.

2014-01-01

Synthesis and patterning of carbon nanomaterials cost effectively is a challenge in electronic and energy storage devices. Here report a one-step, scalable approach for producing and patterning porous graphene films with 3-dimensional networks from commercial polymer films using a CO2 infrared laser. The sp3-carbon atoms are photothermally converted to sp2-carbon atoms by pulsed laser irradiation. The resulting laser-induced graphene (LIG) exhibits high electrical conductivity. The LIG can be readily patterned to interdigitated electrodes for in-plane microsupercapacitors with specific capacitances of >4 mF·cm−2 and power densities of ~9 mW·cm−2. Theoretical calculations partially suggest that enhanced capacitance may result from LIG’s unusual ultra-polycrystalline lattice of pentagon-heptagon structures. Combined with the advantage of one-step processing of LIG in air from commercial polymer sheets, which would allow the employment of a roll-to-roll manufacturing process, this technique provides a rapid route to polymer-written electronic and energy storage devices. PMID:25493446

Four one-dimensional lanthanide-phenylacetate polymers exhibiting luminescence and magnetic cooling/spin-glass behavior.

PubMed

Li, Zhong-Yi; Xu, Ya-Lan; Zhang, Xiang-Fei; Zhai, Bin; Zhang, Fu-Li; Zhang, Jian-Jun; Zhang, Chi; Li, Su-Zhi; Cao, Guang-Xiu

2017-12-21

Four isostructural lanthanide coordination polymers with a phenylacetate (PAA - ) ligand, [Ln(PAA) 3 (H 2 O)] n (Ln = Eu (1); Gd (2); Tb (3); Dy (4)), were synthesized under hydrothermal conditions. Complexes 1-4 display a one-dimensional (1D) wave chain structure bridged by the carboxylate of the PAA - ligand, which was generated via the in situ decarboxylation of phenylmalonic acid. Magnetic studies suggest the presence of ferromagnetic LnLn coupling in the 1D chain of 1-4. Meanwhile, 2 has a significant cryogenic magnetocaloric effect with the maximum -ΔS m of 26.73 at 3 K and 7 T, and 3 and 4 show interesting spin-glass behavior, which is rarely reported for Ln-containing complexes. Additionally, the solid-state photophysical properties of 1 and 3 display strong characteristic Eu 3+ and Tb 3+ photoluminescence emission in the visible region, indicating that Eu- and Tb-based luminescence are sensitized by the effective energy transfer from the ligand to the metal centers.

Dispersion and Mechanical Properties of Carbon Nanotube/Polymer Composites via Melt Compounding

NASA Astrophysics Data System (ADS)

Gorga, Russell; Cohen, Robert

2003-03-01

This work is focused on the fabrication of carbon nanotube/ polymer composites via melt compounding. The main objective of this work is to realize the outstanding properties of carbon nanotubes (high modulus, high thermal and electrical conductivity, elastic buckling) at the macroscopic level by blending carbon nanotubes into a polymer matrix. The challenge lies in dispersing these one dimensional nanoparticles in the polymer matrix. Dispersion of the nanotubes in the composites is analyzed via transmission and scanning electron microscopy. Mechanical properties as well as electrical and thermal conductivity are measured as a function of nanotube loading, orientation, and extrusion conditions. Multi-wall nanotube loadings in the range of 1 and 10 wtconcave-downward departures from the linear stress-strain behavior of the unmodified polymer below 5observations are discussed in the context of possible deformation mechanisms for the nanotube composites.

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

Three-dimensional radiation dosimetry using polymer gel and solid radiochromic polymer: From basics to clinical applications

PubMed Central

Watanabe, Yoichi; Warmington, Leighton; Gopishankar, N

2017-01-01

Accurate dose measurement tools are needed to evaluate the radiation dose delivered to patients by using modern and sophisticated radiation therapy techniques. However, the adequate tools which enable us to directly measure the dose distributions in three-dimensional (3D) space are not commonly available. One such 3D dose measurement device is the polymer-based dosimeter, which changes the material property in response to radiation. These are available in the gel form as polymer gel dosimeter (PGD) and ferrous gel dosimeter (FGD) and in the solid form as solid plastic dosimeter (SPD). Those are made of a continuous uniform medium which polymerizes upon irradiation. Hence, the intrinsic spatial resolution of those dosimeters is very high, and it is only limited by the method by which one converts the dose information recorded by the medium to the absorbed dose. The current standard methods of the dose quantification are magnetic resonance imaging, optical computed tomography, and X-ray computed tomography. In particular, magnetic resonance imaging is well established as a method for obtaining clinically relevant dosimetric data by PGD and FGD. Despite the likely possibility of doing 3D dosimetry by PGD, FGD or SPD, the tools are still lacking wider usages for clinical applications. In this review article, we summarize the current status of PGD, FGD, and SPD and discuss the issue faced by these for wider acceptance in radiation oncology clinic and propose some directions for future development. PMID:28396725

Axial point groups: rank 1, 2, 3 and 4 property tensor tables.

PubMed

Litvin, Daniel B

2015-05-01

The form of a physical property tensor of a quasi-one-dimensional material such as a nanotube or a polymer is determined from the material's axial point group. Tables of the form of rank 1, 2, 3 and 4 property tensors are presented for a wide variety of magnetic and non-magnetic tensor types invariant under each point group in all 31 infinite series of axial point groups. An application of these tables is given in the prediction of the net polarization and magnetic-field-induced polarization in a one-dimensional longitudinal conical magnetic structure in multiferroic hexaferrites.

Crack healing in cross-ply composites observed by dynamic mechanical analysis

NASA Astrophysics Data System (ADS)

Nielsen, Christian; Nemat-Nasser, Sia

2015-03-01

Cross-ply composites with healable polymer matrices are characterized using dynamic mechanical analysis (DMA). The [90,0]s samples are prepared by embedding layers of unidirectional glass or carbon fibers in 2MEP4FS, a polymer with thermally reversible covalent cross-links, which has been shown to be capable of healing internal cracks and fully recovering fracture toughness when the crack surfaces are kept in contact. After fabrication, cracks in the composites' transverse plies are observed due to residual thermal stresses introduced during processing. Single cantilever bending DMA measurements show the samples exhibit periods of increasing storage moduli with increasing temperature. These results are accurately modeled as a one-dimensional composite, which captures the underlying physics of the phenomenon. The effect of cracks on the stiffness is accounted for by a shear-lag model. The predicted crack density of the glass fiber composite is shown to fall within a range observed from microscopy images. Crack healing occurs as a function of temperature, with chemistry and mechanics-based rationales given for the onset and conclusion of healing. The model captures the essential physics of the phenomenon and yields results in accord with experimental observations.

Kinematically stable bipedal locomotion using ionic polymer-metal composite actuators

NASA Astrophysics Data System (ADS)

Hosseinipour, Milad; Elahinia, Mohammad

2013-08-01

Ionic conducting polymer-metal composites (abbreviated as IPMCs) are interesting actuators that can act as artificial muscles in robotic and microelectromechanical systems. Various black or gray box models have modeled the electrochemical-mechanical behavior of these materials. In this study, the governing partial differential equation of the behavior of IPMCs is solved using finite element methods to find the critical actuation parameters, such as strain distribution, maximum strain, and response time. One-dimensional results of the FEM solution are then extended to 2D to find the tip displacement of a flap actuator and experimentally verified. A model of a seven-degree-of-freedom biped robot, actuated by IPMC flaps, is then introduced. The possibility of fast and stable bipedal locomotion using IPMC artificial muscles is the main motivation of this study. Considering the actuator limits, joint path trajectories are generated to achieve a fast and smooth motion. The stability of the proposed gait is then evaluated using the ZMP criterion and motion simulation. The fabrication parameters of each actuator, such as length, platinum plating thickness and installation angle, are then determined using the generated trajectories. A discussion on future studies on force-torque generation of IPMCs for biped locomotion concludes this paper.

Synthesis and characterization of two new zinc(II) coordination polymers with bidentate flexible ligands: Formation of a 2D structure with (44.62)-sql topology

NASA Astrophysics Data System (ADS)

Lalegani, Arash; Khaledi Sardashti, Mohammad; Gajda, Roman; Woźniak, Krzysztof

2017-12-01

Zinc(II) coordination polymers [Zn(bip)2(NCS)2]n (1) and [Zn(μ-bbd)(N3)2]n (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd) and 1,3-bis(imidazolyl)propane (bip), mono-anionic NCS- or N3-ligand and zinc(II) chloride salts. The results of the X-ray analyses demonstrate that in the structure of 1, the zinc(II) ion is located on an inversion center and exhibits an ZnN6 octahedral arrangement while, in the structure of 2, the zinc(II) ion adopts an ZnN4 tetrahedral geometry. In the polymer 1, the NCS groups are terminally N-bonded to the metal center and the each bip with anti-gauche conformation acts as bridging connecting four zinc(II) ions to form a two-dimensional network with a sql [point symbol (44.62)] topology while, in the polymer 1, the N3 groups are terminally bonded to the metal center and each bbd with anti-anti-anti conformation acts as bridging ligand connecting two zinc(II) ions to form a one-dimensional zig-zag chain. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analyses of polymers were also presented.

Effect of Branching on Rod-coil Polyimides as Membrane Materials for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Cubon, Valerie A.; Scheiman, Daniel A.; Bennett, William R.

2003-01-01

This paper describes a series of rod-coil block co-polymers that produce easy to fabricate, dimensionally stable films with good ionic conductivity down to room temperature for use as electrolytes for lithium polymer batteries. The polymers consist of short, rigid rod polyimide segments, alternating with flexible, polyalkylene oxide coil segments. The highly incompatible rods and coils should phase separate, especially in the presence of lithium ions. The coil phase would allow for conduction of lithium ions, while the rigid rod phase would provide a high degree of dimensional stability. An optimization study was carried out to study the effect of four variables (degree of branching, formulated molecular weight, polymerization solvent and lithium salt concentration) on ionic conductivity, glass transition temperature and dimensional stability in this system.

Programmable Control in Extracellular Matrix-mimicking Polymer Hydrogels.

PubMed

Hof, Kevin S; Bastings, Maartje M C

2017-06-28

The extracellular matrix (ECM) and cells have a reciprocal relationship, one shapes the other and vice versa. One of the main challenges of synthetic material systems for developmental cell culturing, organoid and stem cell work includes the implementation of this reciprocal nature. The largest hurdle to achieve true cell-instructive materials in biomaterials engineering is a lack of spatial and temporal control over material properties and the display of bioactive signals compared to the natural cell environment. ECM-mimicking hydrogels have been developed using a wide range of polymers, assembly and cross-linking strategies. While our synthetic toolbox is larger than nature, often our systems underperform when compared to ECM systems with natural components like Matrigel. Material properties and three-dimensional structure ill-represent the three-dimensional ECM reciprocal nature and ligand presentation is an oversimplified version of the complexity found in nature. We hypothesize that the lack of programmable control in properties and ligand presentation forms the basis of this mismatch in performance and analyze the presence of control in current state of the art ECM-mimicking systems based on covalent, supramolecular and recombinant polymers. We conclude that through combining the dynamics of supramolecular materials, robustness from covalent systems and the programmable spatial control of bio-activation in recombinant ECM materials, the optimal synthetic artificial ECM could be assembled.

Effects of polymers on the spatial structure of turbulent flows

NASA Astrophysics Data System (ADS)

Sinhuber, Michael; Ballouz, Joseph G.; Ouellette, Nicholas T.

2017-11-01

It is well known that the addition of minor amounts of polymers to a turbulent water flow can significantly change its properties. One of the most prominent effects is the observed drastic reduction of drag in wall-bounded flows that is utilized in many engineering applications. Much of the research on polymers in turbulence has focused on their influence on the turbulent energy cascade and their interaction with the energy transfer processes. Much less investigated are their effects on the spatial structure of turbulent flows. In a classical von-Kárman swirling flow setup, we used Lagrangian particle tracking to obtain three-dimensional particle trajectories, velocities, and accelerations and find that polymers have a significant effect on Lagrangian measures of the turbulence structure such as radial distribution functions and the curvature of particle trajectories. We find that not only do the statistical distributions change, but also that polymers appear to affect the spatial statistics well beyond the size of the polymers themselves.

Role of Polymer-grafted Nanoparticle Interactions in Supercrystal Self-Assembly

NASA Astrophysics Data System (ADS)

Horst, Nathan; Waltmann, Curt; Travesset, Alex

Many successful strategies are available for the programmable self-assembly of nanoparticle superlattices. In this talk, we discuss the the case of nanoparticles with grafted polymer ligands. For very short polymers, the phase diagram is rationalized by borrowing results from hard-sphere packing models. Although a clear correlation exists between the maximum of the packing fraction of hard spheres and supercrystal equilibrium phases found experimentally, these systems are flexible, which leads to clear deviations from the sphere packing model. Using theoretical and computational models, we present an investigation of the interactions of polymer-grafted nanoparticles, focusing on the role of the rigidity of the chain, and how it affects the resulting two and three-dimensional superlattice structures. Comparison with an experimental system of gold nanoparticles grafted with polyethylene glycol is also presented. Supported by the U.S. Department of Energy (U.S. DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering. Ames Laboratory is operated for the U.S. DOE by Iowa State University under Contract No. DE-AC02-07CH11358.

Heat- and light-induced thiol-ene oligomerization of soybean oil-based polymercaptan

USDA-ARS?s Scientific Manuscript database

Polymercaptanized soybean oil (PMSO), the product of a thiol-ene reaction between soybean oil and hydrogen sulfide, is a material of interest as a lubricant additive and polymer precursor. We investigated with gel permeation chromatography, nuclear magnetic resonance (one-dimensional and two-dimensi...

Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds-synthesis, X-Ray studies and magnetic properties

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

Machura, B., E-mail: basia@ich.us.edu.pl; Switlicka, A.; Zwolinski, P.

2013-01-15

Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH){sub 4}Hg(SCN){sub 4}]{sub n} (1) [Cu(indH){sub 4}Hg(SCN){sub 4}]{sub n} (2) and [Cu(ampy){sub 2}Hg(SCN){sub 4}]{sub n} (3), have one-dimensional coordination structure. Two compounds [Cu(pzH){sub 2}Hg(SCN){sub 4}]{sub n} (4) and [Cu(abzimH)Hg(SCN){sub 4}]{sub n} (5) form two-dimensional nets, whereas the complexes [Cu(pyCN){sub 2}Hg(SCN){sub 4}]{sub n} (6) and [Cu(pyCH(OH)(OMe)){sub 2}Hg(SCN){sub 4}]{sub n} (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the threemore » dimensional net. In 2 the N-H Bullet Bullet Bullet S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H Bullet Bullet Bullet N and N-H Bullet Bullet Bullet S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the three dimensional net. - Graphical abstract: Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compound-synthesis,X-Ray studies and magnetic properties. Highlights: Black-Right-Pointing-Pointer Novel heterobimetallic Cu/Hg coordination polymers were synthesised. Black-Right-Pointing-Pointer The multidimensional structures have been proved by single X-ray analysIs. Black-Right-Pointing-Pointer A variation in the crystalline architectures was observed depending on auxiliary ligands. Black-Right-Pointing-Pointer Magnetic measurements indicate weak exchange interaction between Cu(II) in the crystal lattices below 10 K.« less

Three-dimensional patterning in polymer optical waveguides using focused ion beam milling

NASA Astrophysics Data System (ADS)

Kruse, Kevin; Burrell, Derek; Middlebrook, Christopher

2016-07-01

Waveguide (WG) photonic-bridge taper modules are designed for symmetric planar coupling between silicon WGs and single-mode fibers (SMFs) to minimize photonic chip and packaging footprint requirements with improving broadband functionality. Micromachined fabrication and evaluation of polymer WG tapers utilizing high-resolution focused ion beam (FIB) milling is performed and presented. Polymer etch rates utilizing the FIB and optimal methods for milling polymer tapers are identified for three-dimensional patterning. Polymer WG tapers with low sidewall roughness are manufactured utilizing FIB milling and optically tested for fabrication loss. FIB platforms utilize a focused beam of ions (Ga+) to etch submicron patterns into substrates. Fabricating low-loss polymer WG taper prototypes with the FIB before moving on to mass-production techniques provides theoretical understanding of the polymer taper and its feasibility for connectorization devices between silicon WGs and SMFs.

Interdiffusion of Polycarbonate in Fused Deposition Modeling Welds

NASA Astrophysics Data System (ADS)

Seppala, Jonathan; Forster, Aaron; Satija, Sushil; Jones, Ronald; Migler, Kalman

2015-03-01

Fused deposition modeling (FDM), a now common and inexpensive additive manufacturing method, produces 3D objects by extruding molten polymer layer-by-layer. Compared to traditional polymer processing methods (injection, vacuum, and blow molding), FDM parts have inferior mechanical properties, surface finish, and dimensional stability. From a polymer processing point of view the polymer-polymer weld between each layer limits the mechanical strength of the final part. Unlike traditional processing methods, where the polymer is uniformly melted and entangled, FDM welds are typically weaker due to the short time available for polymer interdiffusion and entanglement. To emulate the FDM process thin film bilayers of polycarbonate/d-polycarbonate were annealed using scaled times and temperatures accessible in FDM. Shift factors from Time-Temperature Superposition, measured by small amplitude oscillatory shear, were used to calculate reasonable annealing times (min) at temperatures below the actual extrusion temperature. The extent of interdiffusion was then measured using neutron reflectivity. Analogous specimens were prepared to characterize the mechanical properties. FDM build parameters were then related to interdiffusion between welded layers and mechanical properties. Understating the relationship between build parameters, interdiffusion, and mechanical strength will allow FDM users to print stronger parts in an intelligent manner rather than using trial-and-error and build parameter lock-in.

Depth-enhanced three-dimensional-two-dimensional convertible display based on modified integral imaging.

PubMed

Park, Jae-Hyeung; Kim, Hak-Rin; Kim, Yunhee; Kim, Joohwan; Hong, Jisoo; Lee, Sin-Doo; Lee, Byoungho

2004-12-01

A depth-enhanced three-dimensional-two-dimensional convertible display that uses a polymer-dispersed liquid crystal based on the principle of integral imaging is proposed. In the proposed method, a lens array is located behind a transmission-type display panel to form an array of point-light sources, and a polymer-dispersed liquid crystal is electrically controlled to pass or to scatter light coming from these point-light sources. Therefore, three-dimensional-two-dimensional conversion is accomplished electrically without any mechanical movement. Moreover, the nonimaging structure of the proposed method increases the expressible depth range considerably. We explain the method of operation and present experimental results.

The effect of dimensionality of nanostructured carbon on the architecture of organic-inorganic hybrid materials.

PubMed

Misra, R D K; Depan, D; Shah, J

2013-08-21

The natural tendency of carbon nanotubes (CNTs) to agglomerate is an underlying reason that prevents the realization of their full potential. On the other hand, covalent functionalization of CNTs to control dispersion leads to disruption of π-conjugation in CNTs and the non-covalent functionalization leads to a weak CNT-polymer interface. To overcome these challenges, we describe the characteristics of fostering of direct nucleation of polymers on nanostructured carbon (CNTs of diameters (~2-200 nm), carbon nanofibers (~200-300 nm), and graphene), which culminates in interfacial adhesion, resulting from electrostatic and van der Waals interaction in the hybrid nanostructured carbon-polymer architecture. Furthermore, the structure is tunable through a change in undercooling. High density polyethylene and polypropylene were selected as two model polymers and two sets of experiments were carried out. The first set of experiments was carried out using CNTs of diameter ~2-5 nm to explore the effect of undercooling and polymer concentration. The second set of experiments was focused on studying the effect of dimensionality on geometrical confinements. The periodic crystallization of polyethylene on small diameter CNTs is demonstrated to be a consequence of the geometrical confinement effect, rather than epitaxy, such that petal-like disks nucleate on large diameter CNTs, carbon nanofibers, and graphene. The application of the process is illustrated in terms of fabricating a system for cellular uptake and bioimaging.

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

Coherent photoluminescence excitation spectroscopy of semicrystalline polymeric semiconductors

NASA Astrophysics Data System (ADS)

Silva, Carlos; Grégoire, Pascal; Thouin, Félix

In polymeric semiconductors, the competition between through-bond (intrachain) and through-space (interchain) electronic coupling determines two-dimensional spatial coherence of excitons. The balance of intra- and interchain excitonic coupling depends very sensitively on solid-state microstructure of the polymer film (polycrystalline, semicrystalline with amorphous domains, etc.). Regioregular poly(3-hexylthiophene) has emerged as a model material because its photoluminescence (PL) spectral lineshape reveals intricate information on the magnitude of excitonic coupling, the extent of energetic disorder, and on the extent to which the disordered energy landscape is correlated. I discuss implementation of coherent two-dimensional electronic spectroscopy. We identify cross peaks between 0-0 and 0-1 excitation peaks, and we measure their time evolution, which we interpret within the context of a hybrid HJ aggregate model. By measurement of the homogeneous linewidth in diverse polymer microstructures, we address the nature of optical transitions within such hynbrid aggregate model. These depend strongly on sample processing, and I discuss the relationship between microstructure, steady-state absorption and PL spectral lineshape, and 2D coherent PL excitation spectral lineshapes.

Ultrafast decoherence dynamics govern photocarrier generation efficiencies in polymer solar cells

PubMed Central

Vella, Eleonora; Li, Hao; Grégoire, Pascal; Tuladhar, Sachetan M.; Vezie, Michelle S.; Few, Sheridan; Bazán, Claudia M.; Nelson, Jenny; Silva-Acuña, Carlos; Bittner, Eric R.

2016-01-01

All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the twodimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20 fs or less. PMID:27412119

Castable three-dimensional stationary phase for electric field-driven applications

DOEpatents

Shepodd, Timothy J.; Whinnery, Jr., Leroy; Even, Jr., William R.

2005-01-25

A polymer material useful as the porous dielectric medium for microfluidic devices generally and electrokinetic pumps in particular. The polymer material is produced from an inverse (water-in-oil) emulsion that creates a 3-dimensional network characterized by small pores and high internal volume, characteristics that are particularly desirable for the dielectric medium for electrokinetic pumps. Further, the material can be cast-to-shape inside a microchannel. The use of bifunctional monomers provides for charge density within the polymer structure sufficient to support electroosmotic flow. The 3-dimensional polymeric material can also be covalently bound to the channel walls thereby making it suitable for high-pressure applications.

Castable three-dimensional stationary phase for electric field-driven applications

DOEpatents

Shepodd, Timothy J [Livermore, CA; Whinnery, Jr., Leroy; Even, Jr., William R.

2009-02-10

A polymer material useful as the porous dielectric medium for microfluidic devices generally and electrokinetic pumps in particular. The polymer material is produced from an inverse (water-in-oil) emulsion that creates a 3-dimensional network characterized by small pores and high internal volume, characteristics that are particularly desirable for the dielectric medium for electrokinetic pumps. Further, the material can be cast-to-shape inside a microchannel. The use of bifunctional monomers provides for charge density within the polymer structure sufficient to support electroosmotic flow. The 3-dimensional polymeric material can also be covalently bound to the channel walls thereby making it suitable for high-pressure applications.

Combustion of a polymer (PMMA) sphere in microgravity

NASA Technical Reports Server (NTRS)

Yang, Jiann C.; Hamins, Anthony

1995-01-01

Polymer combustion is a highly complicated process where chemical reactions may occur not only in the gas phase, but also in the condensed phase as well as at the solid-gas interphase. The chemistry depends strongly on the coupling between the condensed phase and gas phase phenomena. For some polymers, additional complications arise due to the formation of char layers. For others, the behavior of the condensed phase involves swelling, bubbling, melting, sputtering, and multi-stage combustion. Some of these features bear resemblance to the phenomena observed in coal particle combustion. In addition to its relevance to spacecraft fire safety, the combustion of polymeric materials is related to many applications including solid and hybrid rocket propulsion, and of recent interest, waste incineration . The burning rate is one of the most important parameters used to characterize the combustion of polymers. It has been used to rank the polymer flammability under the same experimental conditions and to evaluate various modes of inhibiting polymer flammability. The main objective of this work is to measure the burning rates of a polymeric material in low gravity. Because of inherent logistical difficulties involved in microgravity experiments, it is impossible to examine a wide spectrum of polymeric materials. It is desirable to investigate a polymer whose combustion is less complicated, and yet will lead to a better understanding of the burning characteristics of other more complicated materials. Therefore, a typical non-charring polymer is selected for use in this experimental study. PMMA (polymethylmethacrylate) has been chosen because its thermo-physical properties are well characterized. Although the combustion of PMMA has been extensively studied in 1G experiments, only a limited amount of work has been conducted in low gravity. A spherical sample geometry is chosen in this study because it is the simplest configuration in terms of the microgravity hardware design requirements. Furthermore, a burning PMMA sphere in microgravity represents a one-dimensional flame with overall combustion characteristics expected to be analogous to the combustion of a liquid fuel droplet, a field with many well-developed theories and models. However, differences can also be expected such as the flame-front standoff ratios and the condensed phase processes occurring during combustion.

O'Connell's process as a vicious Brownian motion.

PubMed

Katori, Makoto

2011-12-01

Vicious Brownian motion is a diffusion scaling limit of Fisher's vicious walk model, which is a system of Brownian particles in one dimension such that if two motions meet they kill each other. We consider the vicious Brownian motions conditioned never to collide with each other and call it noncolliding Brownian motion. This conditional diffusion process is equivalent to the eigenvalue process of the Hermitian-matrix-valued Brownian motion studied by Dyson [J. Math. Phys. 3, 1191 (1962)]. Recently, O'Connell [Ann. Probab. (to be published)] introduced a generalization of the noncolliding Brownian motion by using the eigenfunctions (the Whittaker functions) of the quantum Toda lattice in order to analyze a directed polymer model in 1 + 1 dimensions. We consider a system of one-dimensional Brownian motions with a long-ranged killing term as a generalization of the vicious Brownian motion and construct the O'Connell process as a conditional process of the killing Brownian motions to survive forever.

Flexible Skins Containing Integrated Sensors and Circuitry

NASA Technical Reports Server (NTRS)

Liu, Chang

2007-01-01

Artificial sensor skins modeled partly in imitation of biological sensor skins are undergoing development. These sensor skins comprise flexible polymer substrates that contain and/or support dense one- and two-dimensional arrays of microscopic sensors and associated microelectronic circuits. They afford multiple tactile sensing modalities for measuring physical phenomena that can include contact forces; hardnesses, temperatures, and thermal conductivities of objects with which they are in contact; and pressures, shear stresses, and flow velocities in fluids. The sensor skins are mechanically robust, and, because of their flexibility, they can be readily attached to curved and possibly moving and flexing surfaces of robots, wind-tunnel models, and other objects that one might seek to equip for tactile sensing. Because of the diversity of actual and potential sensor-skin design criteria and designs and the complexity of the fabrication processes needed to realize the designs, it is not possible to describe the sensor-skin concept in detail within this article.

Novel polymer-free iridescent lamellar hydrogel for two-dimensional confined growth of ultrathin gold membranes

NASA Astrophysics Data System (ADS)

Niu, Jian; Wang, Dong; Qin, Haili; Xiong, Xiong; Tan, Pengli; Li, Youyong; Liu, Rui; Lu, Xuxing; Wu, Jian; Zhang, Ting; Ni, Weihai; Jin, Jian

2014-02-01

Hydrogels are generally thought to be formed by nano- to micrometre-scale fibres or polymer chains, either physically branched or entangled with each other to trap water. Although there are also anisotropic hydrogels with apparently ordered structures, they are essentially polymer fibre/discrete polymer chains-based network without exception. Here we present a type of polymer-free anisotropic lamellar hydrogels composed of 100-nm-thick water layers sandwiched by two bilayer membranes of a self-assembled nonionic surfactant, hexadecylglyceryl maleate. The hydrogels appear iridescent as a result of Bragg’s reflection of visible light from the periodic lamellar plane. The particular lamellar hydrogel with extremely wide water spacing was used as a soft two-dimensional template to synthesize single-crystalline nanosheets in the confined two-dimensional space. As a consequence, flexible, ultrathin and large area single-crystalline gold membranes with atomically flat surface were produced in the hydrogel. The optical and electrical properties were detected on a single gold membrane.

Measurement of pO2 and pH in Living Breast Tumor Models with Three-Dimensional Resolution by Multiphoton Microscopy during Combined Therapy with Herceptin

DTIC Science & Technology

2007-04-01

contact with a freshly spin-coated NC–titania pre- polymer , which was transferred to a hot plate to initiate polymerization . The pattern of the PDMS stamp...to quantify pO2 and pH in vivo with high three-dimensional resolution (~1 µm3) and significant depth penetration (up to 400 µm) with MPLSM. The...proposed to develop techniques for measuring in vivo pO2 and pH of HER2-positive and negative primary tumors in murine models of breast cancer using

Orbitals, Occupation Numbers, and Band Structure of Short One-Dimensional Cadmium Telluride Polymers.

PubMed

Valentine, Andrew J S; Talapin, Dmitri V; Mazziotti, David A

2017-04-27

Recent work found that soldering CdTe quantum dots together with a molecular CdTe polymer yielded field-effect transistors with much greater electron mobility than quantum dots alone. We present a computational study of the CdTe polymer using the active-space variational two-electron reduced density matrix (2-RDM) method. While analogous complete active-space self-consistent field (CASSCF) methods scale exponentially with the number of active orbitals, the active-space variational 2-RDM method exhibits polynomial scaling. A CASSCF calculation using the (48o,64e) active space studied in this paper requires 10 24 determinants and is therefore intractable, while the variational 2-RDM method in the same active space requires only 2.1 × 10 7 variables. Natural orbitals, natural-orbital occupations, charge gaps, and Mulliken charges are reported as a function of polymer length. The polymer, we find, is strongly correlated, despite possessing a simple sp 3 -hybridized bonding scheme. Calculations reveal the formation of a nearly saturated valence band as the polymer grows and a charge gap that decreases sharply with polymer length.

Computer simulation of heterogeneous polymer photovoltaic devices

NASA Astrophysics Data System (ADS)

Kodali, Hari K.; Ganapathysubramanian, Baskar

2012-04-01

Polymer-based photovoltaic devices have the potential for widespread usage due to their low cost per watt and mechanical flexibility. Efficiencies close to 9.0% have been achieved recently in conjugated polymer based organic solar cells (OSCs). These devices were fabricated using solvent-based processing of electron-donating and electron-accepting materials into the so-called bulk heterojunction (BHJ) architecture. Experimental evidence suggests that a key property determining the power-conversion efficiency of such devices is the final morphological distribution of the donor and acceptor constituents. In order to understand the role of morphology on device performance, we develop a scalable computational framework that efficiently interrogates OSCs to investigate relationships between the morphology at the nano-scale with the device performance. In this work, we extend the Buxton and Clarke model (2007 Modelling Simul. Mater. Sci. Eng. 15 13-26) to simulate realistic devices with complex active layer morphologies using a dimensionally independent, scalable, finite-element method. We incorporate all stages involved in current generation, namely (1) exciton generation and diffusion, (2) charge generation and (3) charge transport in a modular fashion. The numerical challenges encountered during interrogation of realistic microstructures are detailed. We compare each stage of the photovoltaic process for two microstructures: a BHJ morphology and an idealized sawtooth morphology. The results are presented for both two- and three-dimensional structures.

Capillary flow enhancement in rectangular polymer microchannels with a deformable wall.

PubMed

Anoop, R; Sen, A K

2015-07-01

We report the capillary flow enhancement in rectangular polymer microchannels, when one of the channel walls is a deformable polymer membrane. We provide detailed insight into the physics of elastocapillary interaction between the capillary flow and elastic membrane, which leads to significant improvements in capillary flow performance. As liquid flows by capillary action in such channels, the deformable wall deflects inwards due to the Young-Laplace pressure drop across the liquid meniscus. This, in turn, decreases the radius of curvature of the meniscus and increases the driving capillary pressure. A theoretical model is proposed to predict the resultant increase in filling speed and rise height, respectively, in deformable horizontal and vertical microchannels having large aspect ratios. A non-dimensional parameter J, which represents the ratio of the capillary force to the mechanical restoring force, is identified to quantify the elastocapillary effects in terms of the improvement in filling speed (for J>0.238) and the condition for channel collapse (J>1). The theoretical predictions show good agreement with experimental data obtained using deformable rectangular poly(dimethylsiloxane) microchannels. Both model predictions and experimental data show that over 15% improvement in the Washburn coefficient in horizontal channels, and over 30% improvement in capillary rise height in vertical channels, are possible prior to channel collapse. The proposed technique of using deformable membranes as channel walls is a viable method for capillary flow enhancement in microfluidic devices.

Theoretical and computational validation of the Kuhn barrier friction mechanism in unfolded proteins.

PubMed

Avdoshenko, Stanislav M; Das, Atanu; Satija, Rohit; Papoian, Garegin A; Makarov, Dmitrii E

2017-03-21

A long time ago, Kuhn predicted that long polymers should approach a limit where their global motion is controlled by solvent friction alone, with ruggedness of their energy landscapes having no consequences for their dynamics. In contrast, internal friction effects are important for polymers of modest length. Internal friction in proteins, in particular, affects how fast they fold or find their binding targets and, as such, has attracted much recent attention. Here we explore the molecular origins of internal friction in unfolded proteins using atomistic simulations, coarse-grained models and analytic theory. We show that the characteristic internal friction timescale is directly proportional to the timescale of hindered dihedral rotations within the polypeptide chain, with a proportionality coefficient b that is independent of the chain length. Such chain length independence of b provides experimentally testable evidence that internal friction arises from concerted, crankshaft-like dihedral rearrangements. In accord with phenomenological models of internal friction, we find the global reconfiguration timescale of a polypeptide to be the sum of solvent friction and internal friction timescales. At the same time, the time evolution of inter-monomer distances within polypeptides deviates both from the predictions of those models and from a simple, one-dimensional diffusion model.

Comparisons between thermodynamic and one-dimensional combustion models of spark-ignition engines

NASA Technical Reports Server (NTRS)

Ramos, J. I.

1986-01-01

Results from a one-dimensional combustion model employing a constant eddy diffusivity and a one-step chemical reaction are compared with those of one-zone and two-zone thermodynamic models to study the flame propagation in a spark-ignition engine. One-dimensional model predictions are found to be very sensitive to the eddy diffusivity and reaction rate data. The average mixing temperature found using the one-zone thermodynamic model is higher than those of the two-zone and one-dimensional models during the compression stroke, and that of the one-dimensional model is higher than those predicted by both thermodynamic models during the expansion stroke. The one-dimensional model is shown to predict an accelerating flame even when the front approaches the cold cylinder wall.

Doubly self-consistent field theory of grafted polymers under simple shear in steady state

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

Suo, Tongchuan; Whitmore, Mark D., E-mail: mark-whitmore@umanitoba.ca

2014-03-21

We present a generalization of the numerical self-consistent mean-field theory of polymers to the case of grafted polymers under simple shear. The general theoretical framework is presented, and then applied to three different chain models: rods, Gaussian chains, and finitely extensible nonlinear elastic (FENE) chains. The approach is self-consistent at two levels. First, for any flow field, the polymer density profile and effective potential are calculated self-consistently in a manner similar to the usual self-consistent field theory of polymers, except that the calculation is inherently two-dimensional even for a laterally homogeneous system. Second, through the use of a modified Brinkmanmore » equation, the flow field and the polymer profile are made self-consistent with respect to each other. For all chain models, we find that reasonable levels of shear cause the chains to tilt, but it has very little effect on the overall thickness of the polymer layer, causing a small decrease for rods, and an increase of no more than a few percent for the Gaussian and FENE chains. Using the FENE model, we also probe the individual bond lengths, bond correlations, and bond angles along the chains, the effects of the shear on them, and the solvent and bonded stress profiles. We find that the approximations needed within the theory for the Brinkman equation affect the bonded stress, but none of the other quantities.« less

Exact Calculation of the Thermodynamics of Biomacromolecules on Cubic Recursive Lattice.

NASA Astrophysics Data System (ADS)

Huang, Ran

The thermodynamics of biomacromolecules featured as foldable polymer with inner-linkage of hydrogen bonds, e. g. protein, RNA and DNA, play an impressive role in either physical, biological, and polymer sciences. By treating the foldable chains to be the two-tolerate self-avoiding trails (2T polymer), abstract lattice modeling of these complex polymer systems to approach their thermodynamics and subsequent bio-functional properties have been developed for decades. Among these works, the calculations modeled on Bethe and Husimi lattice have shown the excellence of being exactly solvable. Our project extended this effort into the 3D situation, i.e. the cubic recursive lattice. The preliminary exploration basically confirmed others' previous findings on the planar structure, that we have three phases in the grand-canonical phase diagram, with a 1st order transition between non-polymerized and polymer phases, and a 2nd order transition between two distinguishable polymer phases. However the hydrogen bond energy J, stacking energy ɛ, and chain rigidity energy H play more vigorous effects on the thermal behaviors, and this is hypothesized to be due to the larger number of possible configurations provided by the complicated 3D model. By the so far progress, the calculation of biomacromolecules may be applied onto more complex recursive lattices, such as the inhomogeneous lattice to describe the cross-dimensional situations, and beside the thermal properties of the 2T polymers, we may infer some interesting insights of the mysterious folding problem itself. National Natural Science Foundation of China.

Polymer deformation in Brownian ratchets: theory and molecular dynamics simulations.

PubMed

Kenward, Martin; Slater, Gary W

2008-11-01

We examine polymers in the presence of an applied asymmetric sawtooth (ratchet) potential which is periodically switched on and off, using molecular dynamics (MD) simulations with an explicit Lennard-Jones solvent. We show that the distribution of the center of mass for a polymer in a ratchet is relatively wide for potential well depths U0 on the order of several kBT. The application of the ratchet potential also deforms the polymer chains. With increasing U0 the Flory exponent varies from that for a free three-dimensional (3D) chain, nu=35 (U0=0), to that corresponding to a 2D compressed (pancake-shaped) polymer with a value of nu=34 for moderate U0. This has the added effect of decreasing a polymer's diffusion coefficient from its 3D value D3D to that of a pancaked-shaped polymer moving parallel to its minor axis D2D. The result is that a polymer then has a time-dependent diffusion coefficient D(t) during the ratchet off time. We further show that this suggests a different method to operate a ratchet, where the off time of the ratchet, toff, is defined in terms of the relaxation time of the polymer, tauR. We also derive a modified version of the Bader ratchet model [Bader, Proc. Natl. Acad. Sci. U.S.A. 96, 13165 (1999)] which accounts for this deformation and we present a simple expression to describe the time dependent diffusion coefficient D(t). Using this model we then illustrate that polymer deformation can be used to modulate polymer migration in a ratchet potential.

Formation of the –N(NO)N(NO)– polymer at high pressure and stabilization at ambient conditions

PubMed Central

Xiao, Hai; An, Qi; Goddard, William A.; Liu, Wei-Guang; Zybin, Sergey V.

2013-01-01

A number of exotic structures have been formed through high-pressure chemistry, but applications have been hindered by difficulties in recovering the high-pressure phase to ambient conditions (i.e., one atmosphere and 300 K). Here we use dispersion-corrected density functional theory [PBE-ulg (Perdew-Burke-Ernzerhof flavor of DFT with the universal low gradient correction for long range London dispersion)] to predict that above 60 gigapascal (GPa) the most stable form of N2O (the laughing gas in its molecular form) is a one-dimensional polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03∼0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions, both polymers relax below 14 GPa to the same stable nonplanar trans-polymer. The predicted phonon spectrum and dissociation kinetics validates the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a type of conducting nonlinear optical polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions (very high pressure or temperature). PMID:23503849

Identifying Nanoscale Structure-Function Relationships Using Multimodal Atomic Force Microscopy, Dimensionality Reduction, and Regression Techniques.

PubMed

Kong, Jessica; Giridharagopal, Rajiv; Harrison, Jeffrey S; Ginger, David S

2018-05-31

Correlating nanoscale chemical specificity with operational physics is a long-standing goal of functional scanning probe microscopy (SPM). We employ a data analytic approach combining multiple microscopy modes, using compositional information in infrared vibrational excitation maps acquired via photoinduced force microscopy (PiFM) with electrical information from conductive atomic force microscopy. We study a model polymer blend comprising insulating poly(methyl methacrylate) (PMMA) and semiconducting poly(3-hexylthiophene) (P3HT). We show that PiFM spectra are different from FTIR spectra, but can still be used to identify local composition. We use principal component analysis to extract statistically significant principal components and principal component regression to predict local current and identify local polymer composition. In doing so, we observe evidence of semiconducting P3HT within PMMA aggregates. These methods are generalizable to correlated SPM data and provide a meaningful technique for extracting complex compositional information that are impossible to measure from any one technique.

Fibroblast Growth Factor-based Signaling through Synthetic Heparan Sulfate Blocks Copolymers Studied Using High Cell Density Three-dimensional Cell Printing*

PubMed Central

Sterner, Eric; Masuko, Sayaka; Li, Guoyun; Li, Lingyun; Green, Dixy E.; Otto, Nigel J.; Xu, Yongmei; DeAngelis, Paul L.; Liu, Jian; Dordick, Jonathan S.; Linhardt, Robert J.

2014-01-01

Four well-defined heparan sulfate (HS) block copolymers containing S-domains (high sulfo group content) placed adjacent to N-domains (low sulfo group content) were chemoenzymatically synthesized and characterized. The domain lengths in these HS block co-polymers were ∼40 saccharide units. Microtiter 96-well and three-dimensional cell-based microarray assays utilizing murine immortalized bone marrow (BaF3) cells were developed to evaluate the activity of these HS block co-polymers. Each recombinant BaF3 cell line expresses only a single type of fibroblast growth factor receptor (FGFR) but produces neither HS nor fibroblast growth factors (FGFs). In the presence of different FGFs, BaF3 cell proliferation showed clear differences for the four HS block co-polymers examined. These data were used to examine the two proposed signaling models, the symmetric FGF2-HS2-FGFR2 ternary complex model and the asymmetric FGF2-HS1-FGFR2 ternary complex model. In the symmetric FGF2-HS2-FGFR2 model, two acidic HS chains bind in a basic canyon located on the top face of the FGF2-FGFR2 protein complex. In this model the S-domains at the non-reducing ends of the two HS proteoglycan chains are proposed to interact with the FGF2-FGFR2 protein complex. In contrast, in the asymmetric FGF2-HS1-FGFR2 model, a single HS chain interacts with the FGF2-FGFR2 protein complex through a single S-domain that can be located at any position within an HS chain. Our data comparing a series of synthetically prepared HS block copolymers support a preference for the symmetric FGF2-HS2-FGFR2 ternary complex model. PMID:24563485

A predictive model for failure properties of thermoset resins

NASA Technical Reports Server (NTRS)

Caruthers, James M.; Bowles, Kenneth J.

1989-01-01

A predictive model for the three-dimensional failure behavior of engineering polymers has been developed in a recent NASA-sponsored research program. This model acknowledges the underlying molecular deformation mechanisms and thus accounts for the effects of different chemical compositions, crosslink density, functionality of the curing agent, etc., on the complete nonlinear stress-strain response including yield. The material parameters required by the model can be determined from test-tube quantities of a new resin in only a few days. Thus, we can obtain a first-order prediction of the applicability of a new resin for an advanced aerospace application without synthesizing the large quantities of material needed for failure testing. This technology will effect order-of-magnitude reductions in the time and expense required to develop new engineering polymers.

Interactive graphical system for small-angle scattering analysis of polydisperse systems

NASA Astrophysics Data System (ADS)

Konarev, P. V.; Volkov, V. V.; Svergun, D. I.

2016-09-01

A program suite for one-dimensional small-angle scattering analysis of polydisperse systems and multiple data sets is presented. The main program, POLYSAS, has a menu-driven graphical user interface calling computational modules from ATSAS package to perform data treatment and analysis. The graphical menu interface allows one to process multiple (time, concentration or temperature-dependent) data sets and interactively change the parameters for the data modelling using sliders. The graphical representation of the data is done via the Winteracter-based program SASPLOT. The package is designed for the analysis of polydisperse systems and mixtures, and permits one to obtain size distributions and evaluate the volume fractions of the components using linear and non-linear fitting algorithms as well as model-independent singular value decomposition. The use of the POLYSAS package is illustrated by the recent examples of its application to study concentration-dependent oligomeric states of proteins and time kinetics of polymer micelles for anticancer drug delivery.

From 1D Polymers to 2D Polymers: Preparation of Free-Standing Single-Monomer-Thick Two-Dimensional Conjugated Polymers in Water.

PubMed

Zhang, Na; Wang, Taisheng; Wu, Xing; Jiang, Chen; Zhang, Taiming; Jin, Bangkun; Ji, Hengxing; Bai, Wei; Bai, Ruke

2017-07-25

Recently, investigation on two-dimensional (2D) organic polymers has made great progress, and conjugated 2D polymers already play a dynamic role in both academic and practical applications. However, a convenient, noninterfacial approach to obtain single-layer 2D polymers in solution, especially in aqueous media, remains challenging. Herein, we present a facile, highly efficient, and versatile "1D to 2D" strategy for preparation of free-standing single-monomer-thick conjugated 2D polymers in water without any aid. The 2D structure was achieved by taking advantage of the side-by-side self-assembly of a rigid amphiphilic 1D polymer and following topochemical photopolymerization in water. The spontaneous formation of single-layer polymer sheets was driven by synergetic association of the hydrophobic interactions, π-π stacking interactions, and electrostatic repulsion. Both the supramolecular sheets and the covalent sheets were confirmed by spectroscopic analyses and electron microscope techniques. Moreover, in comparison of the supramolecular 2D polymer, the covalent 2D polymer sheets exhibited not only higher mechanical strength but also higher conductivity, which can be ascribed to the conjugated network within the covalent 2D polymer sheets.

Characterization and dynamic charge dependent modeling of conducting polymer trilayer bending

NASA Astrophysics Data System (ADS)

Farajollahi, Meisam; Sassani, Farrokh; Naserifar, Naser; Fannir, Adelyne; Plesse, Cédric; Nguyen, Giao T. M.; Vidal, Frédéric; Madden, John D. W.

2016-11-01

Trilayer bending actuators are charge driven devices that have the ability to function in air and provide large mechanical amplification. The electronic and mechanical properties of these actuators are known to be functions of their charge state making prediction of their responses more difficult when they operate over their full range of deformation. In this work, a combination of state space representation and a two-dimensional RC transmission line model are used to implement a nonlinear time variant model for conducting polymer-based trilayer actuators. Electrical conductivity and Young’s modulus of electromechanically active PEDOT conducting polymer containing films as a function of applied voltage were measured and incorporated into the model. A 16% drop in Young’s modulus and 24 times increase in conductivity are observed by oxidizing the PEDOT. A closed form formulation for radius of curvature of trilayer actuators considering asymmetric and location dependent Young’s modulus and conductivity in the conducting polymer layers is derived and implemented in the model. The nonlinear model shows the capability to predict the radius of curvature as a function of time and position with reasonable consistency (within 4%). The formulation is useful for general trilayer configurations to calculate the radius of curvature as a function of time. The proposed electrochemical modeling approach may also be useful for modeling energy storage devices.

Packaging consideration of two-dimensional polymer-based photonic crystals for laser beam steering

NASA Astrophysics Data System (ADS)

Dou, Xinyuan; Chen, Xiaonan; Chen, Maggie Yihong; Wang, Alan Xiaolong; Jiang, Wei; Chen, Ray T.

2009-02-01

In this paper, we report the theoretical study of polymer-based photonic crystals for laser beam steering which is based on the superprism effect as well as the experiment fabrication of the two dimensional photonic crystals for the laser beam steering. Superprism effect, the principle for beam steering, was separately studied in details through EFC (Equifrequency Contour) analysis. Polymer based photonic crystals were fabricated through double exposure holographic interference method using SU8-2007. The experiment results were also reported.

Lift, Drag, and Pressure Distribution Effects Accompanying Drag-Reducing Polymer Injection on Two-Dimensional Hydrofoil

DTIC Science & Technology

1975-10-01

associated with drag- reducing polymers since Wu’s discovery of pump effects in 1969(16) Some of the research has involved tests on propellers finite span...AD-A022 433 LIFT, DRAG, AND PRESSURE DISTRIBUTION EFFECTS ACCOMPANYING DRAG- REDUCING POLYMER INJECTION ON TWO-DIMENSIONAL HYDROFOIL Daniel H. Fruman...et al Hydronautits, IncorponAted "Prepared f’or: Office of Naval Research October 197’ .!. S.IIE KA NTO CmaY - t 093103 A pprove!- for p~thic relpsa

Training and shape retention in conducting polymer artificial muscles

NASA Astrophysics Data System (ADS)

Tominaga, Kazuo; Hashimoto, Hikaru; Takashima, Wataru; Kaneto, Keiichi

2011-12-01

Electrochemomechanical deformation (ECMD) of the conducting polymer polyaniline film is studied to investigate the behaviour of actuation under tensile loads. The ECMD was induced by the strains due to the insertion of ionic species (cyclic strain) and a creep due to applied loads during the redox cycle. The cyclic strain was enhanced by the experience of high tensile loads, indicating a training effect. The training effect was explained by the enhanced electrochemical activity of the film. The creep was recovered by removal of the tensile load and several electrochemical cycles. This fact indicates that the creep results from the one-dimensional anisotropic deformation, and is retained (shape retention) by the ionic crosslink. The recovery of creep results from the elastic relaxation of the polymer conformation.

Three-dimensionally ordered array of air bubbles in a polymer film

NASA Technical Reports Server (NTRS)

Srinivasarao, M.; Collings, D.; Philips, A.; Patel, S.; Brown, C. S. (Principal Investigator)

2001-01-01

We report the formation of a three-dimensionally ordered array of air bubbles of monodisperse pore size in a polymer film through a templating mechanism based on thermocapillary convection. Dilute solutions of a simple, coil-like polymer in a volatile solvent are cast on a glass slide in the presence of moist air flowing across the surface. Evaporative cooling and the generation of an ordered array of breath figures leads to the formation of multilayers of hexagonally packed water droplets that are preserved in the final, solid polymer film as spherical air bubbles. The dimensions of these bubbles can be controlled simply by changing the velocity of the airflow across the surface. When these three-dimensionally ordered macroporous materials have pore dimensions comparable to the wavelength of visible light, they are of interest as photonic band gaps and optical stop-bands.

Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy.

PubMed

Janko, Marek; Jocher, Michael; Boehm, Alexander; Babel, Laura; Bump, Steven; Biesalski, Markus; Meckel, Tobias; Stark, Robert W

2015-07-13

The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.

Transient Response of a PEM Fuel Cell Representing Variable Load for a Moving Vehicle on Urban Roads

DOT National Transportation Integrated Search

2001-01-01

Three-dimensional numerical simulation of transient response of a Polymer Electrolyte Membrane (PEM) fuel cell subjected to a variable load is developed. The model parameters are typical of experimental cell for a 10-cm2 reactive area with serpentine...

Quantitative NDE applied to composites and metals

NASA Technical Reports Server (NTRS)

Heyman, Joseph S.; Winfree, William P.; Parker, F. Raymond; Heath, D. Michele; Welch, Christopher S.

1989-01-01

Research at the NASA/Langley Research Center concerning quantitative NDE of composites and metals is reviewed. The relationship between ultrasonics and polymer cure is outlined. NDE models are presented, which can be used to develop measurement technologies for characterizing the curing of a polymer system for composite materials. The models can be used to determine the glass transition temperature, the degree of cure, and the cure rate. The application of the model to control autoclave processing of composite materials is noted. Consideration is given to the use of thermal diffusion models combined with controlled thermal input measurements to determine the thermal diffusivity of materials. Also, a two-dimensional physical model is described that permits delaminations in samples of Space Shuttle Solid Rocket Motors to be detected in thermograms in the presence of cooling effects and uneven heating.

Facile and green preparation of novel adsorption materials by combining sol-gel with ion imprinting technology for selective removal of Cu(II) ions from aqueous solution

NASA Astrophysics Data System (ADS)

Ren, Zhongqi; Zhu, Xinyan; Du, Jian; Kong, Delong; Wang, Nian; Wang, Zhuo; Wang, Qi; Liu, Wei; Li, Qunsheng; Zhou, Zhiyong

2018-03-01

A novel green adsorption polymer was prepared by ion imprinted technology in conjunction with sol-gel process under mild conditions for the selective removal of Cu(II) ions from aqueous solution. Effects of preparation conditions on adsorption performance of prepared polymers were studied. The ion-imprinted polymer was prepared using Cu(II) ion as template, N-[3-(2-aminoethylamino) propyl] trimethoxysilane (AAPTMS) as functional monomer and tetraethyl orthosilicate (TEOS) as cross-linker. Water was used as solvent in the whole preparation process. The imprinted and non-imprinted polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM), Brunauer, Emmett and Teller (BET) and zeta potential. Three-dimensional network structure was formed and functional monomer was successfully cross-linked into the network structure of polymers. Effects of adsorption conditions on adsorption performance of prepared polymers were studied too. The pH value is of great influence on adsorption behavior. Adsorption by ion-imprinted polymer was fast (adsorption equilibrium was reached within 60 min). The adsorption capacity of Cu(II) ion-imprinted polymer was always larger than that of non-imprinted polymer. Pseudo-second-order kinetics model and Freundlich isotherm model fitted well with adsorption data. The maximum adsorption capacity of Cu(II) ion-imprinted polymer was 39.82 mg·g-1. However, the preparation conditions used in this work are much milder than those reported in literatures. The Cu(II) ion-imprinted polymer showed high selectivity and relative selectivity coefficients for Pb(II), Ni(II), Cd(II) and Co(II). In addition, the prepared ion-imprinted polymer could be reused several times without significant loss of adsorption capacity.

Exciton size and binding energy limitations in one-dimensional organic materials

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

Kraner, S., E-mail: stefan.kraner@iapp.de; Koerner, C.; Leo, K.

2015-12-28

In current organic photovoltaic devices, the loss in energy caused by the charge transfer step necessary for exciton dissociation leads to a low open circuit voltage, being one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy to a value of the order of thermal energy, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley-Queisser limit. We determine the size of the excitons for different organic molecules and polymers by time dependent densitymore » functional theory calculations. For optically relevant transitions, the exciton size saturates around 0.7 nm for one-dimensional molecules with a size longer than about 4 nm. For the ladder-type polymer poly(benzimidazobenzophenanthroline), we obtain an exciton binding energy of about 0.3 eV, serving as a lower limit of the exciton binding energy for the organic materials investigated. Furthermore, we show that charge transfer transitions increase the exciton size and thus identify possible routes towards a further decrease of the exciton binding energy.« less

Rapid Stencil Mask Fabrication Enabled One-Step Polymer-Free Graphene Patterning and Direct Transfer for Flexible Graphene Devices

PubMed Central

Yong, Keong; Ashraf, Ali; Kang, Pilgyu; Nam, SungWoo

2016-01-01

We report a one-step polymer-free approach to patterning graphene using a stencil mask and oxygen plasma reactive-ion etching, with a subsequent polymer-free direct transfer for flexible graphene devices. Our stencil mask is fabricated via a subtractive, laser cutting manufacturing technique, followed by lamination of stencil mask onto graphene grown on Cu foil for patterning. Subsequently, micro-sized graphene features of various shapes are patterned via reactive-ion etching. The integrity of our graphene after patterning is confirmed by Raman spectroscopy. We further demonstrate the rapid prototyping capability of a stretchable, crumpled graphene strain sensor and patterned graphene condensation channels for potential applications in sensing and heat transfer, respectively. We further demonstrate that the polymer-free approach for both patterning and transfer to flexible substrates allows the realization of cleaner graphene features as confirmed by water contact angle measurements. We believe that our new method promotes rapid, facile fabrication of cleaner graphene devices, and can be extended to other two dimensional materials in the future. PMID:27118249

Nanowires and Nanostructures That Grow Like Polymer Molecules

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

Shaw, Santosh; Cademartiri, Ludovico

Unique properties (e.g., rubber elasticity, viscoelasticity, folding, reptation) determine the utility of polymer molecules and derive from their morphology (i.e., one-dimensional connectivity and large aspect ratios) and flexibility. Crystals do not display similar properties because they have smaller aspect ratios, they are rigid, and they are often too large and heavy to be colloidally stable. We argue, with the support of recent experimental studies, that these limitations are not fundamental and that they might be overcome by growth processes that mimic polymerization. Furthermore, we (i) discuss the similarities between crystallization and polymerization, (ii) critically review the existing experimental evidence ofmore » polymer-like growth kinetic and behavior in crystals and nanostructures, and (iii) propose heuristic guidelines for the synthesis of “polymer-like” crystals and assemblies. Understanding these anisotropic materials at the boundary between molecules and solids will determine whether we can confer the unique properties of polymer molecules to crystals, expanding them with topology, dynamics, and information and not just tuning them with size.« less

Modeling electrical response of polymer-coated SAW resonators by equivalent circuit representation.

PubMed

Kshetrimayum, Roshan; Yadava, R D S; Tandon, R P

2011-07-01

The paper presents an equivalent circuit model of the polymer coated surface acoustic wave (SAW) resonators by combining coupling-of-mode (COM) description of SAW resonators and perturbation calculation of SAW propagation under polymer loading. An expression for the motional load produced by polymer coating is deduced in terms of COM parameters and polymer characteristics. In addition, expressions for the shifts in resonance frequency and attenuation due to polymer loading are obtained. Simulation results are presented for one-port and two-port resonator devices coated with viscoelastic thin polymer film. The influence of polymer film on resonator response is studied with regard to variations in film thickness and shear modulus. The model simplifies understanding of polymer-coated SAW sensors. Copyright © 2010 Elsevier B.V. All rights reserved.

Two Dimensional Polymer That Generates Nitric Oxide.

DOEpatents

McDonald, William F.; Koren, Amy B.

2005-10-04

A polymeric composition that generates nitric oxide and a process for rendering the surface of a substrate nonthrombogenic by applying a coating of the polymeric composition to the substrate are disclosed. The composition comprises: (1) a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, and (ii) a crosslinking agent containing functional groups capable of reacting with the amino groups; and (2) a plurality of nitric oxide generating functional groups associated with the crosslinked chemical combination. Once exposed to a physiological environment, the coating generates nitric oxide thereby inhibiting platelet aggregation. In one embodiment, the nitric oxide generating functional groups are provided by a nitrated compound (e.g., nitrocellulose) imbedded in the polymeric composition. In another embodiment, the nitric oxide generating functional groups comprise N2O2- groups covalently bonded to amino groups on the polymer.

Freestanding, heat resistant microporous film for use in energy storage devices

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

Pekala, Richard W.; Cherukupalli, Srinivas; Waterhouse, Robert R.

Preferred embodiments of a freestanding, heat resistant microporous polymer film (10) constructed for use in an energy storage device (70, 100) implements one or more of the following approaches to exhibit excellent high temperature mechanical and dimensional stability: incorporation into a porous polyolefin film of sufficiently high loading levels of inorganic or ceramic filler material (16) to maintain porosity (18) and achieve low thermal shrinkage; use of crosslinkable polyethylene to contribute to crosslinking the polymer matrix (14) in a highly inorganic material-filled polyolefin film; and heat treating or annealing of biaxially oriented, highly inorganic material-filled polyolefin film above the meltingmore » point temperature of the polymer matrix to reduce residual stress while maintaining high porosity. The freestanding, heat resistant microporous polymer film embodiments exhibit extremely low resistance, as evidenced by MacMullin numbers of less than 4.5.« less

[Preparation and evaluation of novel mesoporous molecular sieve of baicalin surface molecularly imprinted polymers].

PubMed

Gu, Xia-li; He, Hong-liang; Shi, Li-ying; Gao, Yan-kun; Chen, Li-na

2015-05-01

Taking mesoporous molecular sieve MCM-41 as a substrate, baicalin (BA) as template, acrylamide (AM) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, ethanol as solvent, under thermal polymerization initiator of azobis isobutyronitrilo (AIBN) , a kind of selective recognition of baicalin surface molecularly imprinted polymer was synthesized. The surface morphologies and characteristics of the MIPs were characterized by infrared spectroscopy (IR) and transmission electron microscope (TEM). The adsorption properties of polymer microsphere for the template were tested by the dynamic adsorption equilibrium experiments and static adsorption equilibrium experiments. The experiment showed that the imprinting process was successfully and the well-ordered one-dimensional pore structure of MCM-41 was still preserved. Furthermore, molecularly imprinted polymers had higher selective ability for BA, then provided a new method for the efficient separation and enrichment of baicalin active ingredients from medicinal plants Scutellaria baicalensis.

Electric-Field-Directed Parallel Alignment Architecting 3D Lithium-Ion Pathways within Solid Composite Electrolyte.

PubMed

Liu, Xueqing; Peng, Sha; Gao, Shuyu; Cao, Yuancheng; You, Qingliang; Zhou, Liyong; Jin, Yongcheng; Liu, Zhihong; Liu, Jiyan

2018-05-09

It is of great significance to seek high-performance solid electrolytes via a facile chemistry and simple process for meeting the requirements of solid batteries. Previous reports revealed that ion conducting pathways within ceramic-polymer composite electrolytes mainly occur at ceramic particles and the ceramic-polymer interface. Herein, one facile strategy toward ceramic particles' alignment and assembly induced by an external alternating-current (AC) electric field is presented. It was manifested by an in situ optical microscope that Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 particles and poly(ethylene glycol) diacrylate in poly(dimethylsiloxane) (LATP@PEGDA@PDMS) assembled into three-dimensional connected networks on applying an external AC electric field. Scanning electron microscopy revealed that the ceramic LATP particles aligned into a necklacelike assembly. Electrochemical impedance spectroscopy confirmed that the ionic conductivity of this necklacelike alignment was significantly enhanced compared to that of the random one. It was demonstrated that this facile strategy of applying an AC electric field can be a very effective approach for architecting three-dimensional lithium-ion conductive networks within solid composite electrolyte.

3D printed orodispersible films with Aripiprazole.

PubMed

Jamróz, Witold; Kurek, Mateusz; Łyszczarz, Ewelina; Szafraniec, Joanna; Knapik-Kowalczuk, Justyna; Syrek, Karolina; Paluch, Marian; Jachowicz, Renata

2017-11-30

Three dimensional printing technology is gaining in importance because of its increasing availability and wide applications. One of the three dimensional printing techniques is Fused Deposition Modelling (FDM) which works on the basis of hot melt extrusion-well known in the pharmaceutical technology. Combination of fused deposition modelling with preparation of the orodispersible film with poorly water soluble substance such as aripiprazole seems to be extra advantageous in terms of dissolution rate. 3D printed as well as casted films were compared in terms of physicochemical and mechanical properties. Moreover, drug-free films were prepared to evaluate the impact of the extrusion process and aripiprazole presence on the film properties. X-ray diffractometry and thermal analyses confirmed transition of aripiprazole into amorphous state during film preparation using 3D printing technique. Amorphization of the aripiprazole and porous structure of printed film led to increased dissolution rate in comparison to casted films, which, however have slightly better mechanical properties due to their continuous structure. It can be concluded that fused deposition modelling is suitable technique and polyvinyl alcohol is applicable polymer for orodispersible films preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

Biological implications of lab-on-a-chip devices fabricated using multi-jet modelling and stereolithography processes

NASA Astrophysics Data System (ADS)

Zhu, Feng; Macdonald, Niall; Skommer, Joanna; Wlodkowic, Donald

2015-06-01

Current microfabrication methods are often restricted to two-dimensional (2D) or two and a half dimensional (2.5D) structures. Those fabrication issues can be potentially addressed by emerging additive manufacturing technologies. Despite rapid growth of additive manufacturing technologies in tissue engineering, microfluidics has seen relatively little developments with regards to adopting 3D printing for rapid fabrication of complex chip-based devices. This has been due to two major factors: lack of sufficient resolution of current rapid-prototyping methods (usually >100 μm ) and optical transparency of polymers to allow in vitro imaging of specimens. We postulate that adopting innovative fabrication processes can provide effective solutions for prototyping and manufacturing of chip-based devices with high-aspect ratios (i.e. above ration of 20:1). This work provides a comprehensive investigation of commercially available additive manufacturing technologies as an alternative for rapid prototyping of complex monolithic Lab-on-a-Chip devices for biological applications. We explored both multi-jet modelling (MJM) and several stereolithography (SLA) processes with five different 3D printing resins. Compared with other rapid prototyping technologies such as PDMS soft lithography and infrared laser micromachining, we demonstrated that selected SLA technologies had superior resolution and feature quality. We also for the first time optimised the post-processing protocols and demonstrated polymer features under scanning electronic microscope (SEM). Finally we demonstrate that selected SLA polymers have optical properties enabling high-resolution biological imaging. A caution should be, however, exercised as more work is needed to develop fully bio-compatible and non-toxic polymer chemistries.

Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes.

PubMed

Xu, Chao; Hedin, Niklas; Shi, Hua-Tian; Xin, ZhiFeng; Zhang, Qian-Feng

2015-04-14

Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

Investigation on vascular cytotoxicity and extravascular transport of cationic polymer nanoparticles using perfusable 3D microvessel model.

PubMed

Ahn, Jungho; Cho, Chong-Su; Cho, Seong Woo; Kang, Joo H; Kim, Sung-Yon; Min, Dal-Hee; Song, Joon Myong; Park, Tae-Eun; Jeon, Noo Li

2018-05-25

Vascular networks are the first sites exposed to cationic polymer nanoparticles (NPs) administered intravenously, and thus function as a barrier for NPs reaching the target organ. While cationic polymer NPs have been intensively studied as non-viral delivery systems, their biological effects in human microvessels have been poorly investigated due to a lack of appropriate in vitro systems. Here, we employed a three-dimensional microvessel on a chip, which accurately models in vivo conditions. An open and perfused microvessel surrounded by pericytes was shown to reproduce the important features of living vasculature, including barrier function and biomarkers. Using this microvessel chip, we observed contraction of the microvascular lumen induced by perfused polyethylenimine (PEI)/DNA NPs. We demonstrated that the oxidative stress present when microvessels were exposed to PEI NPs led to rearrangement of microtubules resulting in microvessel contraction. Furthermore, the transcytotic behavior of PEI NPs was analyzed in the microvessel by monitoring the escape of PEI NPs from the microvascular lumen into the perivascular region, which was not possible in two-dimensional culture systems. With our new understanding of the different behaviors of cationic polymer NPs depending on their transcytotic route, we suggest that caveolae-mediated transcytosis is a powerful route for efficient extravascular transport. Microvascular networks are not only biological system constituting largest surface area in the body and but also first site exposed to nanoparticle in vivo. While cationic polymer NPs have been intensively studied as non-viral delivery systems, its biological effects in human microvessel have been poorly investigated due to lack of appropriate in vitro systems. Here, we microengineered an open and perfused 3D pericyte incorporated microvessel model which possesses same morphological characteristic of in vivo. Using the microengineered model, this study represents the first report of transcytotic behavior of NPs in 3D microvessel, and its effect on extravasation efficiency. Our study lays the groundwork for the integration of innovative technologies to examine blood vessel-nanoparticle interaction, which a critical but ill-defined phenomenon. Copyright © 2018. Published by Elsevier Ltd.

Sequential growth for lifetime extension in biomimetic polypyrrole actuator systems

NASA Astrophysics Data System (ADS)

Sarrazin, J. C.; Mascaro, Stephen A.

2015-04-01

Electroactive polymers (EAPs) present prospective use in actuation and manipulation devices due to their low electrical activation requirements, biocompatibility, and mechanical performance. One of the main drawbacks with EAP actuators is a decrease in performance over extended periods of operation caused by over-oxidation of the polymer and general polymer degradation. Synthesis of the EAP material, polypyrrole with an embedded metal helix allows for sequential growth of the polymer during operation. The helical metal electrode acts as a scaffolding to support the polymer, and direct the 3-dimensional change in volume of the polymer along the axis of the helix during oxidative and reductive cycling. The metal helix also provides a working metal electrode through the entire length of the polymer actuator to distribute charge for actuation, as well as for sequential growth steps during the lifetime of operation of the polymer. This work demonstrates the method of sequential growth can be utilized after extended periods of use to partially restore electrical and mechanical performance of polypyrrole actuators. Since the actuation must be temporarily stopped to allow for a sequential growth cycle to be performed and reverse some of the polymer degradation, these actuator systems more closely mimic natural muscle in their analogous maintenance and repair.

Nanoscale Design of Nano-Sized Particles in Shape-Memory Polymer Nanocomposites Driven by Electricity

PubMed Central

Lu, Haibao; Huang, Wei Min; Liang, Fei; Yu, Kai

2013-01-01

In the last few years, we have witnessed significant progress in developing high performance shape memory polymer (SMP) nanocomposites, in particular, for shape recovery activated by indirect heating in the presence of electricity, magnetism, light, radio frequency, microwave and radiation, etc. In this paper, we critically review recent findings in Joule heating of SMP nanocomposites incorporated with nanosized conductive electromagnetic particles by means of nanoscale control via applying an electro- and/or magnetic field. A few different nanoscale design principles to form one-/two-/three- dimensional conductive networks are discussed. PMID:28788303

Non-Traditional Aromatic Topologies and Biomimetic Assembly Motifs as Components of Functional Pi-Conjugated Oligomers

PubMed Central

Tovar, John D.; Diegelmann, Stephen R.; Peart, Patricia A.

2010-01-01

This article will highlight our recent work using conjugated oligomers as precursors to electroactive polymer films and self-assembling nanomaterials. One area of investigation has focused on nonbenzenoid aromaticity in the context of charge delocalization in conjugated polymers. In these studies, polymerizable pi-conjugated units were coupled onto unusual aromatic cores such as methano[10]annulene. This article will also show how biologically-inspired assembly of molecularly well-defined oligopeptides that flank pi-conjugated oligomers has resulted in the aqueous construction of 1-dimensional nanomaterials that encourage electronic delocalization among the pi-electron systems.

Novel octanuclear copper(I) metallomacrocycles and their transformation into hexanuclear 2-dimensional grids of copper(i) coordination polymers containing cyclodiphosphazanes, [(micro-NtBuP)2(NC4H8X)2] (X = NMe, O).

PubMed

Suresh, D; Balakrishna, Maravanji S; Mague, Joel T

2008-07-07

Novel octanuclear copper(I) macrocyclic complexes and hexanuclear 2-dimensional grid-like polymers containing [P(micro-NR)](2) scaffold in which the anionic moieties are trapped inside the cationic macrocyclic cavities are reported.

Photodeposition Method For Fabricating A Three-Dimensional, Patterned Polymer Microstructure

DOEpatents

Walt, David R.; Healey, Brian G.

2001-03-13

The present invention is a photodeposition methodology for fabricating a three-dimensional patterned polymer microstructure. A variety of polymeric structures can be fabricated on solid substrates using unitary fiber optic arrays for light delivery. The methodology allows micrometer-scale photopatterning for the fabricated structures using masks substantially larger than the desired dimensions of the microstructure.

Analytical Modeling for Mechanical Strength Prediction with Raman Spectroscopy and Fractured Surface Morphology of Novel Coconut Shell Powder Reinforced: Epoxy Composites

NASA Astrophysics Data System (ADS)

Singh, Savita; Singh, Alok; Sharma, Sudhir Kumar

2017-06-01

In this paper, an analytical modeling and prediction of tensile and flexural strength of three dimensional micro-scaled novel coconut shell powder (CSP) reinforced epoxy polymer composites have been reported. The novel CSP has a specific mixing ratio of different coconut shell particle size. A comparison is made between obtained experimental strength and modified Guth model. The result shows a strong evidence for non-validation of modified Guth model for strength prediction. Consequently, a constitutive modeled equation named Singh model has been developed to predict the tensile and flexural strength of this novel CSP reinforced epoxy composite. Moreover, high resolution Raman spectrum shows that 40 % CSP reinforced epoxy composite has high dielectric constant to become an alternative material for capacitance whereas fractured surface morphology revealed that a strong bonding between novel CSP and epoxy polymer for the application as light weight composite materials in engineering.

Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

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

Lian, Chen; Liu, Liu; Guo, Xu

2016-01-15

Two novel coordination polymers, namely, [Ca(NCP){sub 2}]{sub ∞} (I) and [Sr(NCP){sub 2}]{sub ∞} (II) were synthesized under hydrothermal conditions based on 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (HNCP) and characterized by elemental analysis, infrared spectrometry, X-ray powder diffraction and single crystal X-ray diffraction. Findings indicate that I and II are isomorphous and isostructural, containing the unit of M(NCP{sup −}){sub 4} (M=Ca(II) and Sr(II)), based on which to assemble into three-dimensional (3D) porous 4-fold interpenetration honeycomb-shaped neutral coordination polymers (CPs). Between the adjacent lamellar structures in I and II, there exist π–π interactions between the pyridine rings belonging to phenanthroline of NCP{sup −} which stabilize themore » frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability. - Graphical abstract: One-dimensional nanotubular channels with the cross dimension of 37.1959(20)×23.6141(11)Å{sup 2} in the three-dimensional honeycomb-shaped coordination network of II are observed. The topological analysis of II indicates that there exists a typical diamond framework possessing large adamantanoid cages, which containing four cyclohexane-shaped patterns in chair conformations. - Highlights: • Two isomorphous and isostructural coordination polymers based on flexible ligand and two alkaline-earth metal salts have been synthesized and characterized. • Structural analysis indicates that I and II are assembled into 3D porous honeycomb-shaped metal-organic frameworks. • Both I and II display stronger fluorescence emissions and higher thermal stability.« less

Temperature Mapping of 3D Printed Polymer Plates: Experimental and Numerical Study

PubMed Central

Kousiatza, Charoula; Chatzidai, Nikoleta; Karalekas, Dimitris

2017-01-01

In Fused Deposition Modeling (FDM), which is a common thermoplastic Additive Manufacturing (AM) method, the polymer model material that is in the form of a flexible filament is heated above its glass transition temperature (Tg) to a semi-molten state in the head’s liquefier. The heated material is extruded in a rastering configuration onto the building platform where it rapidly cools and solidifies with the adjoining material. The heating and rapid cooling cycles of the work materials exhibited during the FDM process provoke non-uniform thermal gradients and cause stress build-up that consequently result in part distortions, dimensional inaccuracy and even possible part fabrication failure. Within the purpose of optimizing the FDM technique by eliminating the presence of such undesirable effects, real-time monitoring is essential for the evaluation and control of the final parts’ quality. The present work investigates the temperature distributions developed during the FDM building process of multilayered thin plates and on this basis a numerical study is also presented. The recordings of temperature changes were achieved by embedding temperature measuring sensors at various locations into the middle-plane of the printed structures. The experimental results, mapping the temperature variations within the samples, were compared to the corresponding ones obtained by finite element modeling, exhibiting good correlation. PMID:28245557

Grazing-incidence small angle x-ray scattering studies of nanoscale polymer gratings

NASA Astrophysics Data System (ADS)

Doxastakis, Manolis; Suh, Hyo Seon; Chen, Xuanxuan; Rincon Delgadillo, Paulina A.; Wan, Lingshu; Williamson, Lance; Jiang, Zhang; Strzalka, Joseph; Wang, Jin; Chen, Wei; Ferrier, Nicola; Ramirez-Hernandez, Abelardo; de Pablo, Juan J.; Gronheid, Roel; Nealey, Paul

2015-03-01

Grazing-Incidence Small Angle X-ray Scattering (GISAXS) offers the ability to probe large sample areas, providing three-dimensional structural information at high detail in a thin film geometry. In this study we exploit the application of GISAXS to structures formed at one step of the LiNe (Liu-Nealey) flow using chemical patterns for directed self-assembly of block copolymer films. Experiments conducted at the Argonne National Laboratory provided scattering patterns probing film characteristics at both parallel and normal directions to the surface. We demonstrate the application of new computational methods to construct models based on scattering measured. Such analysis allows for extraction of structural characteristics at unprecedented detail.

Principles that Govern the Performance of Molecular Motors

NASA Astrophysics Data System (ADS)

Eide, Jon; Chakraborty, Arup; Oster, George

2003-03-01

We have created a two dimensional polymeric coarse-grained model to simulate the power stroke from the F0F1 ATP synthase class of molecular motors. There has been much work to understand the structure and dynamics of this type of molecular motor using both constrained molecular dynamics and general Markov models but neither of them have been able to elucidate in a qualitative manner how a constant force is created and transferred in the motor at a nearly 100efficiency. Our model is a modified Rouse system using Brownian and Monte Carlo (with solvent) Dynamics, concentrating only on the catalytic site and protein structures that we think are important for motor motion and energy transfer. While modeling the real system as closely as possible, we have determined the optimum characteristics for maximum efficiency. The efficiency depends on the load against the polymer, the polymer flexibility, polymer and surface matching, and solvent interactions. Insight into the basic principles behind the mechanical motion of this system may have implications for many other molecular motors driven by nucleotide hydrolysis and help design synthetic devices that can carry out biomimetic tasks.

Novel synthesis strategies for natural polymer and composite biomaterials as potential scaffolds for tissue engineering

PubMed Central

Ko, Hsu-Feng; Sfeir, Charles; Kumta, Prashant N.

2010-01-01

Recent developments in tissue engineering approaches frequently revolve around the use of three-dimensional scaffolds to function as the template for cellular activities to repair, rebuild and regenerate damaged or lost tissues. While there are several biomaterials to select as three-dimensional scaffolds, it is generally agreed that a biomaterial to be used in tissue engineering needs to possess certain material characteristics such as biocompatibility, suitable surface chemistry, interconnected porosity, desired mechanical properties and biodegradability. The use of naturally derived polymers as three-dimensional scaffolds has been gaining widespread attention owing to their favourable attributes of biocompatibility, low cost and ease of processing. This paper discusses the synthesis of various polysaccharide-based, naturally derived polymers, and the potential of using these biomaterials to serve as tissue engineering three-dimensional scaffolds is also evaluated. In this study, naturally derived polymers, specifically cellulose, chitosan, alginate and agarose, and their composites, are examined. Single-component scaffolds of plain cellulose, plain chitosan and plain alginate as well as composite scaffolds of cellulose–alginate, cellulose–agarose, cellulose–chitosan, chitosan–alginate and chitosan–agarose are synthesized, and their suitability as tissue engineering scaffolds is assessed. It is shown that naturally derived polymers in the form of hydrogels can be synthesized, and the lyophilization technique is used to synthesize various composites comprising these natural polymers. The composite scaffolds appear to be sponge-like after lyophilization. Scanning electron microscopy is used to demonstrate the formation of an interconnected porous network within the polymeric scaffold following lyophilization. It is also established that HeLa cells attach and proliferate well on scaffolds of cellulose, chitosan or alginate. The synthesis protocols reported in this study can therefore be used to manufacture naturally derived polymer-based scaffolds as potential biomaterials for various tissue engineering applications. PMID:20308112

Two-dimensional homogeneous isotropic fluid turbulence with polymer additives

NASA Astrophysics Data System (ADS)

Gupta, Anupam; Perlekar, Prasad; Pandit, Rahul

2015-03-01

We carry out an extensive and high-resolution direct numerical simulation of homogeneous, isotropic turbulence in two-dimensional fluid films with air-drag-induced friction and with polymer additives. Our study reveals that the polymers (a) reduce the total fluid energy, enstrophy, and palinstrophy; (b) modify the fluid energy spectrum in both inverse- and forward-cascade régimes; (c) reduce small-scale intermittency; (d) suppress regions of high vorticity and strain rate; and (e) stretch in strain-dominated regions. We compare our results with earlier experimental studies and propose new experiments.

Weighting of topologically different interactions in a model of two-dimensional polymer collapse.

PubMed

Bedini, Andrea; Owczarek, Aleksander L; Prellberg, Thomas

2013-01-01

We study by computer simulation a recently introduced generalized model of self-interacting self-avoiding trails on the square lattice that distinguishes two topologically different types of self-interaction: namely, crossings where the trail passes across itself and collisions where the lattice path visits the same site without crossing. This model generalizes the canonical interacting self-avoiding trail model of polymer collapse, which has a strongly divergent specific heat at its transition point. We confirm the recent prediction that the asymmetry does not affect the universality class for a range of asymmetry. Certainly, where the weighting of collisions outweighs that of crossings this is well supported numerically. When crossings are weighted heavily relative to collisions, the collapse transition reverts to the canonical θ-point-like behavior found in interacting self-avoiding walks.

Low-dimensional quantum magnetism in Cu (NCS) 2: A molecular framework material

NASA Astrophysics Data System (ADS)

Cliffe, Matthew J.; Lee, Jeongjae; Paddison, Joseph A. M.; Schott, Sam; Mukherjee, Paromita; Gaultois, Michael W.; Manuel, Pascal; Sirringhaus, Henning; Dutton, Siân E.; Grey, Clare P.

2018-04-01

Low-dimensional magnetic materials with spin-1/2 moments can host a range of exotic magnetic phenomena due to the intrinsic importance of quantum fluctuations to their behavior. Here, we report the structure, magnetic structure, and magnetic properties of copper ii thiocyanate, Cu(NCS ) 2, a one-dimensional coordination polymer which displays low-dimensional quantum magnetism. Magnetic susceptibility, electron paramagnetic resonance spectroscopy, 13C magic-angle spinning nuclear magnetic resonance spectroscopy, and density functional theory investigations indicate that Cu(NCS ) 2 behaves as a two-dimensional array of weakly coupled antiferromagnetic spin chains [J2=133 (1 ) K , α =J1/J2=0.08 ] . Powder neutron-diffraction measurements confirm that Cu(NCS ) 2 orders as a commensurate antiferromagnet below TN=12 K , with a strongly reduced ordered moment (0.3 μB ) due to quantum fluctuations.

Nanoconfinement: an effective way to enhance PVDF piezoelectric properties.

PubMed

Cauda, Valentina; Stassi, Stefano; Bejtka, Katarzyna; Canavese, Giancarlo

2013-07-10

The dimensional confinement and oriented crystallization are both key factors in determining the piezoelectric properties of a polymeric nanostructured material. Here we prepare arrays of one-dimensional polymeric nanowires showing piezoelectric features by template-wetting two distinct polymers into anodic porous alumina (APA) membranes. In particular, poly(vinylidene fluoride), PVDF, and its copolymer poly(vinylidene fluoride-trifluoroethylene), PVTF, are obtained in commercially available APA, showing a final diameter of about 200 nm and several micrometers in length, reflecting the templating matrix features. We show that the crystallization of both polymers into a ferroelectric phase is directed by the nanotemplate confinement. Interestingly, the PVDF nanowires mainly crystallize into the β-phase in the nanoporous matrix, whereas the reference thin film of PVDF crystallizes in the α nonpolar phase. In the case of the PVTF nanowires, needle-like crystals oriented perpendicularly to the APA channel walls are observed, giving insight on the molecular orientation of the polymer within the nanowire structure. A remarkable piezoelectric behavior of both 1-D polymeric nanowires is observed, upon recording ferroelectric polarization, hysteresis, and displacement loops. In particular, an outstanding piezoelectric effect is observed for the PVDF nanowires with respect to the polymeric thin film, considering that no poling was carried out. Current versus voltage (I-V) characteristics showed a consistent switching behavior of the ferroelectric polar domains, thus revealing the importance of the confined and oriented crystallization of the polymer in monodimensional nanoarchitectures.

Physics of Quantum Structures in Photovoltaic Devices

NASA Technical Reports Server (NTRS)

Raffaelle, Ryne P.; Andersen, John D.

2005-01-01

There has been considerable activity recently regarding the possibilities of using various nanostructures and nanomaterials to improve photovoltaic conversion of solar energy. Recent theoretical results indicate that dramatic improvements in device efficiency may be attainable through the use of three-dimensional arrays of zero-dimensional conductors (i.e., quantum dots) in an ordinary p-i-n solar cell structure. Quantum dots and other nanostructured materials may also prove to have some benefits in terms of temperature coefficients and radiation degradation associated with space solar cells. Two-dimensional semiconductor superlattices have already demonstrated some advantages in this regard. It has also recently been demonstrated that semiconducting quantum dots can also be used to improve conversion efficiencies in polymeric thin film solar cells. Improvement in thin film cells utilizing conjugated polymers has also be achieved through the use of one-dimensional quantum structures such as carbon nanotubes. It is believed that carbon nanotubes may contribute to both the disassociation as well as the carrier transport in the conjugated polymers used in certain thin film photovoltaic cells. In this paper we will review the underlying physics governing some of the new photovoltaic nanostructures being pursued, as well as the the current methods being employed to produce III-V, II-VI, and even chalcopyrite-based nanomaterials and nanostructures for solar cells.

A threefold interpenetrated two-dimensional zinc(II) supramolecular architecture based on 3-nitrobenzoic acid and 4,4'-bipyridine.

PubMed

Tang, Long; Wang, Ji-Jiang; Fu, Feng; Wang, Sheng-Wen; Liu, Qi-Rui

2016-02-01

With regard to crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal-organic coordination polymers. The critical factor for the construction of coordination polymers is the rational choice of the organic building blocks and the metal centre. The reaction of Zn(OAc)2·2H2O (OAc is acetate) with 3-nitrobenzoic acid (HNBA) and 4,4'-bipyridine (4,4'-bipy) under hydrothermal conditions produced a two-dimensional zinc(II) supramolecular architecture, catena-poly[[bis(3-nitrobenzoato-κ(2)O,O')zinc(II)]-μ-4,4'-bipyridine-κ(2)N:N'], [Zn(C7H4NO4)2(C10H8N2)]n or [Zn(NBA)2(4,4'-bipy)]n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction analysis. The Zn(II) ions are connected by the 4,4'-bipy ligands to form a one-dimensional zigzag chain and the chains are decorated with anionic NBA ligands which interact further through aromatic π-π stacking interactions, expanding the structure into a threefold interpenetrated two-dimensional supramolecular architecture. The solid-state fluorescence analysis indicates a slight blue shift compared with pure 4,4'-bipyridine and HNBA.

Modeling Anisotropic Self-Assembly of Isotropic Objects: from Hairy Nanoparticles to Methylcellulose Fibrils

NASA Astrophysics Data System (ADS)

Ginzburg, Valeriy

Spontaneous symmetry breaking and formation of anisotropic structures from apparently isotropic building blocks is an exciting and not fully understood topic. I will discuss two examples of such self-assembly. The first example is related to the assembly of ``hairy'' nanoparticles in homopolymer matrices. The particles can assemble into long strings (they can also form other morphologies, as well) even though the shape of each particle and the distribution of ligands on the particle surface is spherically symmetric. Using the approach developed by Thompson, Ginzburg, Matsen, and Balazs, we show that presence of other particles can re-distribute the ligands and effectively ``polarize'' the particle-particle interaction, giving rise to the formation of 1d particle strings. In the second example, we consider aqueous solutions of methylcellulose (MC) polymers. It has been shown recently that at high temperature, the polymers form high-aspect ratio ``fibrils'' with diameter ~15 nm and length in the hundreds on nanometers. Using coarse-grained Molecular Dynamics (CG-MD), we propose that the ``fibrils'' are result of one-dimensional self-assembly of single molecule ``rings''. Each MC polymer chain is forced into a ring because of the balance between internal chain rigidity (favoring more expanded configuration) and unfavorable polymer-water interactions (favoring more collapsed conformation). We also develop a theory predicting rheology and phase behavior of aqueous MC, and validate it against experimental data. Both examples show that anisotropic self-assembly can show up in unexpected places, and various theoretical tools are needed to successfully model it. Funded by The Dow Chemical Company through Grant 223278AF. Collaborators: R. L. Sammler (Dow), W. Huang and R. Larson (U. of Michigan).

Command Surface of Self-Organizing Structures by Radical Polymers with Cooperative Redox Reactivity.

PubMed

Sato, Kan; Mizuma, Takahiro; Nishide, Hiroyuki; Oyaizu, Kenichi

2017-10-04

Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched in response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10 3 ). The switching enabled both a rapid cell response and long charge retention. Such a cooperative command surface of self-assembled structures will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.

High sensitivity gas sensor based on high-Q suspended polymer photonic crystal nanocavity

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

Clevenson, Hannah, E-mail: hannahac@mit.edu; Desjardins, Pierre; Gan, Xuetao

2014-06-16

We present high-sensitivity, multi-use optical gas sensors based on a one-dimensional photonic crystal cavity. These devices are implemented in versatile, flexible polymer materials which swell when in contact with a target gas, causing a measurable cavity length change. This change causes a shift in the cavity resonance, allowing precision measurements of gas concentration. We demonstrate suspended polymer nanocavity sensors and the recovery of sensors after the removal of stimulant gas from the system. With a measured quality factor exceeding 10{sup 4}, we show measurements of gas concentration as low as 600 parts per million (ppm) and an experimental sensitivity ofmore » 10 ppm; furthermore, we predict detection levels in the parts-per-billion range for a variety of gases.« less

Wave propagation in viscoelastic horns using a fractional calculus rheology model

NASA Astrophysics Data System (ADS)

Margulies, Timothy

2003-10-01

The complex mechanical behavior of materials are characterized by fluid and solid models with fractional calculus differentials to relate stress and strain fields. Fractional derivatives have been shown to describe the viscoelastic stress from polymer chain theory for molecular solutions [Rouse and Sittel, J. Appl. Phys. 24, 690 (1953)]. Here the propagation of infinitesimal waves in one dimensional horns with a small cross-sectional area change along the longitudinal axis are examined. In particular, the linear, conical, exponential, and catenoidal shapes are studied. The wave amplitudes versus frequency are solved analytically and predicted with mathematical computation. Fractional rheology data from Bagley [J. Rheol. 27, 201 (1983); Bagley and Torvik, J. Rheol. 30, 133 (1986)] are incorporated in the simulations. Classical elastic and fluid ``Webster equations'' are recovered in the appropriate limits. Horns with real materials that employ fractional calculus representations can be modeled to examine design trade-offs for engineering or for scientific application.

Comparison of two-dimensional and quasi-one-dimensional scramjet models by the example of VAG experiment

NASA Astrophysics Data System (ADS)

Seleznev, R. K.

2017-02-01

In the paper two-dimensional and quasi-one dimensional models for scramjet combustion chamber are described. Comparison of the results of calculations for the two-dimensional and quasi-one dimensional code by the example of VAG experiment are presented.

Reduced viscosity interpreted for fluid/gas mixtures

NASA Technical Reports Server (NTRS)

Lewis, D. H.

1981-01-01

Analysis predicts decrease in fluid viscosity by comparing pressure profile of fluid/gas mixture with that of power-law fluid. Fluid is taken to be viscous, non-Newtonian, and incompressible; the gas to be ideal; the flow to be inertia-free, isothermal, and one dimensional. Analysis assists in design of flow systems for petroleum, coal, polymers, and other materials.

Observation of the Chiral and Achiral Hexatic Phases of Self-assembled Micellar polymers

PubMed Central

Pal, Antara; Kamal, Md. Arif; Raghunathan, V. A.

2016-01-01

We report the discovery of a thermodynamically stable line hexatic (N + 6) phase in a three-dimensional (3D) system made up of self-assembled polymer-like micelles of amphiphilic molecules. The experimentally observed phase transition sequence nematic (N)  N + 6  two-dimensional hexagonal (2D-H) is in good agreement with the theoretical predictions. Further, the present study also brings to light the effect of chirality on the N + 6 phase. In the chiral N + 6 phase the bond-orientational order within each “polymer” bundle is found to be twisted about an axis parallel to the average polymer direction. This structure is consistent with the theoretically envisaged Moiré state, thereby providing the first experimental demonstration of the Moiré structure. In addition to confirming the predictions of fundamental theories of two-dimensional melting, these results are relevant in a variety of situations in chemistry, physics and biology, where parallel packing of polymer-like objects are encountered. PMID:27577927

A two-dimensional bilayered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating 1,2-bis(pyridin-4-yl)ethene and 2,2'-(diazenediyl)dibenzoic acid.

PubMed

Liu, Lei-Lei; Zhou, Yan; Li, Ping; Tian, Jiang-Ya

2014-02-01

In poly[[μ2-1,2-bis(pyridin-4-yl)ethene-κ(2)N:N'][μ2-2,2'-(diazenediyl)dibenzoato-κ(3)O,O':O'']cadmium(II)], [Cd(C14H8N2O4)(C12H10N2)]n, the asymmetric unit contains one Cd(II) cation, one 2,2'-(diazenediyl)dibenzoate anion (denoted L(2-)) and one 1,2-bis(pyridin-4-yl)ethene ligand (denoted bpe). Each Cd(II) centre is six-coordinated by four O atoms of bridging/chelating carboxylate groups from three L(2-) ligands and by two N atoms from two bpe ligands, forming a distorted octahedron. The Cd(II) cations are bridged by L(2-) and bpe ligands to give a two-dimensional (4,4) layer. The layers are interlinked through bridging carboxylate O atoms from L(2-) ligands, generating a two-dimensional bilayered structure with a 3(6)4(13)6(2) topology. The bilayered structures are further extended to form a three-dimensional supramolecular architecture via a combination of hydrogen-bonding and aromatic stacking interactions.

Exploring load, velocity, and surface disorder dependence of friction with one-dimensional and two-dimensional models.

PubMed

Dagdeviren, Omur E

2018-08-03

The effect of surface disorder, load, and velocity on friction between a single asperity contact and a model surface is explored with one-dimensional and two-dimensional Prandtl-Tomlinson (PT) models. We show that there are fundamental physical differences between the predictions of one-dimensional and two-dimensional models. The one-dimensional model estimates a monotonic increase in friction and energy dissipation with load, velocity, and surface disorder. However, a two-dimensional PT model, which is expected to approximate a tip-sample system more realistically, reveals a non-monotonic trend, i.e. friction is inert to surface disorder and roughness in wearless friction regime. The two-dimensional model discloses that the surface disorder starts to dominate the friction and energy dissipation when the tip and the sample interact predominantly deep into the repulsive regime. Our numerical calculations address that tracking the minimum energy path and the slip-stick motion are two competing effects that determine the load, velocity, and surface disorder dependence of friction. In the two-dimensional model, the single asperity can follow the minimum energy path in wearless regime; however, with increasing load and sliding velocity, the slip-stick movement dominates the dynamic motion and results in an increase in friction by impeding tracing the minimum energy path. Contrary to the two-dimensional model, when the one-dimensional PT model is employed, the single asperity cannot escape to the minimum energy minimum due to constraint motion and reveals only a trivial dependence of friction on load, velocity, and surface disorder. Our computational analyses clarify the physical differences between the predictions of the one-dimensional and two-dimensional models and open new avenues for disordered surfaces for low energy dissipation applications in wearless friction regime.

Study on Damage Evaluation and Machinability of UD-CFRP for the Orthogonal Cutting Operation Using Scanning Acoustic Microscopy and the Finite Element Method.

PubMed

Wang, Dongyao; He, Xiaodong; Xu, Zhonghai; Jiao, Weicheng; Yang, Fan; Jiang, Long; Li, Linlin; Liu, Wenbo; Wang, Rongguo

2017-02-20

Owing to high specific strength and designability, unidirectional carbon fiber reinforced polymer (UD-CFRP) has been utilized in numerous fields to replace conventional metal materials. Post machining processes are always required for UD-CFRP to achieve dimensional tolerance and assembly specifications. Due to inhomogeneity and anisotropy, UD-CFRP differs greatly from metal materials in machining and failure mechanism. To improve the efficiency and avoid machining-induced damage, this paper undertook to study the correlations between cutting parameters, fiber orientation angle, cutting forces, and cutting-induced damage for UD-CFRP laminate. Scanning acoustic microscopy (SAM) was employed and one-/two-dimensional damage factors were then created to quantitatively characterize the damage of the laminate workpieces. According to the 3D Hashin's criteria a numerical model was further proposed in terms of the finite element method (FEM). A good agreement between simulation and experimental results was validated for the prediction and structural optimization of the UD-CFRP.

Study on Damage Evaluation and Machinability of UD-CFRP for the Orthogonal Cutting Operation Using Scanning Acoustic Microscopy and the Finite Element Method

PubMed Central

Wang, Dongyao; He, Xiaodong; Xu, Zhonghai; Jiao, Weicheng; Yang, Fan; Jiang, Long; Li, Linlin; Liu, Wenbo; Wang, Rongguo

2017-01-01

Owing to high specific strength and designability, unidirectional carbon fiber reinforced polymer (UD-CFRP) has been utilized in numerous fields to replace conventional metal materials. Post machining processes are always required for UD-CFRP to achieve dimensional tolerance and assembly specifications. Due to inhomogeneity and anisotropy, UD-CFRP differs greatly from metal materials in machining and failure mechanism. To improve the efficiency and avoid machining-induced damage, this paper undertook to study the correlations between cutting parameters, fiber orientation angle, cutting forces, and cutting-induced damage for UD-CFRP laminate. Scanning acoustic microscopy (SAM) was employed and one-/two-dimensional damage factors were then created to quantitatively characterize the damage of the laminate workpieces. According to the 3D Hashin’s criteria a numerical model was further proposed in terms of the finite element method (FEM). A good agreement between simulation and experimental results was validated for the prediction and structural optimization of the UD-CFRP. PMID:28772565

Nanoparticles Stabilize Thin Polymer Films: A Fundamental Study to Understand the Phenomenon

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

Michael E. Mackay

2009-03-04

A new understanding of thermodynamics at the nanoscale resulted in a recently discovered first order phase transition that nanoparticles in a polymer film will all segregate to the supporting substrate. This is an unusual phase transition that was predicted using a modeling technique developed at Sandia National Laboratories and required the equivalent of many computational years on one computer. This project is a collaboration between Prof. Michael Mackay's group and Dr. Amalie Frischknecht (Sandia National Laboratories) where experimental observation and theoretical rationalization and prediction are brought together. Other discoveries were that this phase transition could be avoided by changing themore » nanoparticle properties yielding control of the assembly process at the nanoscale. In fact, the nanoparticles could be made to assemble to the supporting substrate, to the air interface or not assemble at all within a thin polymer film of order 100 nm in thickness. However, when the assembly process is present it is so robust that it is possible to make rough liquid films at the nanoscale due to nanoparticles assembling around three-dimensional objects. From this knowledge we are able to design and manufacture new coatings with particular emphasis on polymer-based solar cells. Careful control of the morphology at the nanoscale is expected to provide more efficient devices since the physics of these systems is dictated at this length scale and assembly of nanoparticles to various interfaces is critical to operation.« less

Polymer-mediated nanorod self-assembly predicted by dissipative particle dynamics simulations.

PubMed

Khani, Shaghayegh; Jamali, Safa; Boromand, Arman; Hore, Michael J A; Maia, Joao

2015-09-14

Self-assembly of nanoparticles in polymer matrices is an interesting and growing subject in the field of nanoscience and technology. We report herein on modelling studies of the self-assembly and phase behavior of nanorods in a homopolymer matrix, with the specific goal of evaluating the role of deterministic entropic and enthalpic factors that control the aggregation/dispersion in such systems. Grafting polymer brushes from the nanorods is one approach to control/impact their self-assembly capabilities within a polymer matrix. From an energetic point of view, miscible interactions between the brush and the matrix are required for achieving a better dispersibility; however, grafting density and brush length are the two important parameters in dictating the morphology. Unlike in previous computational studies, the present Dissipative Particle Dynamics (DPD) simulation framework is able to both predict dispersion or aggregation of nanorods and determine the self-assembled structure, allowing for the determination of a phase diagram, which takes all of these factors into account. Three types of morphologies are predicted: dispersion, aggregation and partial aggregation. Moreover, favorable enthalpic interactions between the brush and the matrix are found to be essential for expanding the window for achieving a well-dispersed morphology. A three-dimensional phase diagram is mapped on which all the afore-mentioned parameters are taken into account. Additionally, in the case of immiscibility between brushes and the matrix, simulations predict the formation of some new and tunable structures.

Mechanochemical Synthesis of Carbon Nanothread Single Crystals.

PubMed

Li, Xiang; Baldini, Maria; Wang, Tao; Chen, Bo; Xu, En-Shi; Vermilyea, Brian; Crespi, Vincent H; Hoffmann, Roald; Molaison, Jamie J; Tulk, Christopher A; Guthrie, Malcolm; Sinogeikin, Stanislav; Badding, John V

2017-11-15

Synthesis of well-ordered reduced dimensional carbon solids with extended bonding remains a challenge. For example, few single-crystal organic monomers react under topochemical control to produce single-crystal extended solids. We report a mechanochemical synthesis in which slow compression at room temperature under uniaxial stress can convert polycrystalline or single-crystal benzene monomer into single-crystalline packings of carbon nanothreads, a one-dimensional sp 3 carbon nanomaterial. The long-range order over hundreds of microns of these crystals allows them to readily exfoliate into fibers. The mechanochemical reaction produces macroscopic single crystals despite large dimensional changes caused by the formation of multiple strong, covalent C-C bonds to each monomer and a lack of reactant single-crystal order. Therefore, it appears not to follow a topochemical pathway, but rather one guided by uniaxial stress, to which the nanothreads consistently align. Slow-compression room-temperature synthesis may allow diverse molecular monomers to form single-crystalline packings of polymers, threads, and higher dimensional carbon networks.

One-dimensional ferromagnetic array compound [Co3(SBA)2(OH)2(H2O)2]n, (SBA = 4-sulfobenzoate)

NASA Astrophysics Data System (ADS)

Honda, Zentaro; Nomoto, Naoyuki; Fujihara, Takashi; Hagiwara, Masayuki; Kida, Takanori; Sawada, Yuya; Fukuda, Takeshi; Kamata, Norihiko

2018-06-01

We report on the syntheses, crystal structure, and magnetic properties of the transition metal coordination polymer [Co3(SBA)2(OH)2(H2O)2]n, (SBA = 4-sulfobenzoate) in which CoO6 octahedra are linked through their edges, forming one-dimensional (1D) Co(II) arrays running along the crystal a-axis. These arrays are further perpendicularly bridged by SBA ligand to construct a three-dimensional framework. Its magnetic properties have been investigated, and ferromagnetic interactions within the arrays have been found. From heat capacity measurements, we have found that this compound exhibits a three-dimensional ferromagnetic phase transition at TC = 1.54 K, and the specific heat just above TC shows a Schottky anomaly which originates from an energy gap caused by uniaxial magnetic anisotropy. These results suggest that [Co3(SBA)2(OH)2(H2O)2]n consists of weakly coupled 1D ferromagnetic Ising arrays.

Modeling thermoelectric transport in organic materials.

PubMed

Wang, Dong; Shi, Wen; Chen, Jianming; Xi, Jinyang; Shuai, Zhigang

2012-12-28

Thermoelectric energy converters can directly convert heat to electricity using semiconducting materials via the Seebeck effect and electricity to heat via the Peltier effect. Their efficiency depends on the dimensionless thermoelectric figure of merit of the material, which is defined as zT = S(2)σT/κ with S, σ, κ, and T being the Seebeck coefficient, electrical conductivity, thermal conductivity, and absolute temperature respectively. Organic materials for thermoelectric applications have attracted great attention. In this review, we present our recent progress made in developing theories and computational schemes to predict the thermoelectric figure of merit at the first-principles level. The methods have been applied to model thermoelectric transport in closely-packed molecular crystals and one-dimensional conducting polymer chains. The physical insight gained in these studies will help in the design of efficient organic thermoelectric materials.

Annealed Scaling for a Charged Polymer

NASA Astrophysics Data System (ADS)

Caravenna, F.; den Hollander, F.; Pétrélis, N.; Poisat, J.

2016-03-01

This paper studies an undirected polymer chain living on the one-dimensional integer lattice and carrying i.i.d. random charges. Each self-intersection of the polymer chain contributes to the interaction Hamiltonian an energy that is equal to the product of the charges of the two monomers that meet. The joint probability distribution for the polymer chain and the charges is given by the Gibbs distribution associated with the interaction Hamiltonian. The focus is on the annealed free energy per monomer in the limit as the length of the polymer chain tends to infinity. We derive a spectral representation for the free energy and use this to prove that there is a critical curve in the parameter plane of charge bias versus inverse temperature separating a ballistic phase from a subballistic phase. We show that the phase transition is first order. We prove large deviation principles for the laws of the empirical speed and the empirical charge, and derive a spectral representation for the associated rate functions. Interestingly, in both phases both rate functions exhibit flat pieces, which correspond to an inhomogeneous strategy for the polymer to realise a large deviation. The large deviation principles in turn lead to laws of large numbers and central limit theorems. We identify the scaling behaviour of the critical curve for small and for large charge bias. In addition, we identify the scaling behaviour of the free energy for small charge bias and small inverse temperature. Both are linked to an associated Sturm-Liouville eigenvalue problem. A key tool in our analysis is the Ray-Knight formula for the local times of the one-dimensional simple random walk. This formula is exploited to derive a closed form expression for the generating function of the annealed partition function, and for several related quantities. This expression in turn serves as the starting point for the derivation of the spectral representation for the free energy, and for the scaling theorems. What happens for the quenched free energy per monomer remains open. We state two modest results and raise a few questions.

Characterization of Homopolymer and Polymer Blend Films by Phase Sensitive Acoustic Microscopy

NASA Astrophysics Data System (ADS)

Ngwa, Wilfred; Wannemacher, Reinhold; Grill, Wolfgang

2003-03-01

CHARACTERIZATION OF HOMOPOLYMER AND POLYMER BLEND FILMS BY PHASE SENSITIVE ACOUSTIC MICROSCOPY W Ngwa, R Wannemacher, W Grill Institute of Experimental Physics II, University of Leipzig, 04103 Leipzig, Germany Abstract We have used phase sensitive acoustic microscopy (PSAM) to study homopolymer thin films of polystyrene (PS) and poly (methyl methacrylate) (PMMA), as well as PS/PMMA blend films. We show from our results that PSAM can be used as a complementary and highly valuable technique for elucidating the three-dimensional (3D) morphology and micromechanical properties of thin films. Three-dimensional image acquisition with vector contrast provides the basis for: complex V(z) analysis (per image pixel), 3D image processing, height profiling, and subsurface image analysis of the polymer films. Results show good agreement with previous studies. In addition, important new information on the three dimensional structure and properties of polymer films is obtained. Homopolymer film structure analysis reveals (pseudo-) dewetting by retraction of droplets, resulting in a morphology that can serve as a starting point for the analysis of polymer blend thin films. The outcome of confocal laser scanning microscopy studies, performed on the same samples are correlated with the obtained results. Advantages and limitations of PSAM are discussed.

Creating "hotels" for cells by electrospinning honeycomb-like polymeric structures.

PubMed

Liang, T; Mahalingam, S; Edirisinghe, M

2013-10-01

It is well established that three-dimensional honeycomb-like nanofibrous structures enhance cell activity. In this work, we report that electrospun polymer nanofibres self-assemble into three-dimensional honeycomb-like structures. The underlying mechanism is studied by varying the polymer solution concentration, collecting substrates and working distance. The polymer solution concentration has a significant effect on the size of the electrospun nanofibres. The collection substrate and working distance affect the electric field strength, the evaporation of solvent and the discharging of nanofibres and consequently these two had a significant influence on the self-assembly of nanofibres. © 2013.

O'Connell's process as a vicious Brownian motion

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

Katori, Makoto

Vicious Brownian motion is a diffusion scaling limit of Fisher's vicious walk model, which is a system of Brownian particles in one dimension such that if two motions meet they kill each other. We consider the vicious Brownian motions conditioned never to collide with each other and call it noncolliding Brownian motion. This conditional diffusion process is equivalent to the eigenvalue process of the Hermitian-matrix-valued Brownian motion studied by Dyson [J. Math. Phys. 3, 1191 (1962)]. Recently, O'Connell [Ann. Probab. (to be published)] introduced a generalization of the noncolliding Brownian motion by using the eigenfunctions (the Whittaker functions) of themore » quantum Toda lattice in order to analyze a directed polymer model in 1 + 1 dimensions. We consider a system of one-dimensional Brownian motions with a long-ranged killing term as a generalization of the vicious Brownian motion and construct the O'Connell process as a conditional process of the killing Brownian motions to survive forever.« less

Application of activated barrier hopping theory to viscoplastic modeling of glassy polymers

NASA Astrophysics Data System (ADS)

Sweeney, J.; Spencer, P. E.; Vgenopoulos, D.; Babenko, M.; Boutenel, F.; Caton-Rose, P.; Coates, P. D.

2018-05-01

An established statistical mechanical theory of amorphous polymer deformation has been incorporated as a plastic mechanism into a constitutive model and applied to a range of polymer mechanical deformations. The temperature and rate dependence of the tensile yield of PVC, as reported in early studies, has been modeled to high levels of accuracy. Tensile experiments on PET reported here are analyzed similarly and good accuracy is also achieved. The frequently observed increase in the gradient of the plot of yield stress against logarithm of strain rate is an inherent feature of the constitutive model. The form of temperature dependence of the yield that is predicted by the model is found to give an accurate representation. The constitutive model is developed in two-dimensional form and implemented as a user-defined subroutine in the finite element package ABAQUS. This analysis is applied to the tensile experiments on PET, in some of which strain is localized in the form of shear bands and necks. These deformations are modeled with partial success, though adiabatic heating of the instability causes inaccuracies for this isothermal implementation of the model. The plastic mechanism has advantages over the Eyring process, is equally tractable, and presents no particular difficulties in implementation with finite elements.

Application of activated barrier hopping theory to viscoplastic modeling of glassy polymers

NASA Astrophysics Data System (ADS)

Sweeney, J.; Spencer, P. E.; Vgenopoulos, D.; Babenko, M.; Boutenel, F.; Caton-Rose, P.; Coates, P. D.

2017-10-01

An established statistical mechanical theory of amorphous polymer deformation has been incorporated as a plastic mechanism into a constitutive model and applied to a range of polymer mechanical deformations. The temperature and rate dependence of the tensile yield of PVC, as reported in early studies, has been modeled to high levels of accuracy. Tensile experiments on PET reported here are analyzed similarly and good accuracy is also achieved. The frequently observed increase in the gradient of the plot of yield stress against logarithm of strain rate is an inherent feature of the constitutive model. The form of temperature dependence of the yield that is predicted by the model is found to give an accurate representation. The constitutive model is developed in two-dimensional form and implemented as a user-defined subroutine in the finite element package ABAQUS. This analysis is applied to the tensile experiments on PET, in some of which strain is localized in the form of shear bands and necks. These deformations are modeled with partial success, though adiabatic heating of the instability causes inaccuracies for this isothermal implementation of the model. The plastic mechanism has advantages over the Eyring process, is equally tractable, and presents no particular difficulties in implementation with finite elements.

Polymer Stress-Gradient Induced Migration in Thin Film Flow Over Topography

NASA Astrophysics Data System (ADS)

Tsouka, Sophia; Dimakopoulos, Yiannis; Tsamopoulos, John

2014-11-01

We consider the 2D, steady film flow of a dilute polymer solution over a periodic topography. We examine how the distribution of polymer in the planarization of topographical features is affected by flow intensity and physical properties. The thermodynamically acceptable, Mavrantzas-Beris two-fluid Hamiltonian model is used for polymer migration. The resulting system of differential equations is solved via the mixed FE method combined with an elliptic grid generation scheme. We present numerical results for polymer concentration, stress, velocity and flux of components as a function of the non-dimensional parameters of the problem (Deborah, Peclet, Reynolds and Capillary numbers, ratio of solvent viscosity to total liquid viscosity and geometric features of the topography). Polymer migration to the free surface is enhanced when the cavity gets steeper and deeper. This increases the spatial extent of the polymer depletion layer and induces strong banding in the stresses away from the substrate wall, especially in low polymer concentration. Macromolecules with longer relaxation times are predicted to migrate towards the free surface more easily, while high surface tension combined with a certain range of Reynolds numbers affects the free surface deformations. Work supported by the General Secretariat of Research & Technology of Greece through the program ``Excellence'' (Grant No. 1918) in the framework ``Education and Lifelong Learning'' co-funded by the ESF.

Microtubule organization in three-dimensional confined geometries: evaluating the role of elasticity through a combined in vitro and modeling approach.

PubMed

Cosentino Lagomarsino, Marco; Tanase, Catalin; Vos, Jan W; Emons, Anne Mie C; Mulder, Bela M; Dogterom, Marileen

2007-02-01

Microtubules or microtubule bundles in cells often grow longer than the size of the cell, which causes their shape and organization to adapt to constraints imposed by the cell geometry. We test the reciprocal role of elasticity and confinement in the organization of growing microtubules in a confining box-like geometry, in the absence of other (active) microtubule organizing processes. This is inspired, for example, by the cortical microtubule array of elongating plant cells, where microtubules are typically organized in an aligned array transverse to the cell elongation axis. The method we adopt is a combination of analytical calculations, in which the polymers are modeled as inextensible filaments with bending elasticity confined to a two-dimensional surface that defines the limits of a three-dimensional space, and in vitro experiments, in which microtubules are polymerized from nucleation seeds in microfabricated chambers. We show that these features are sufficient to organize the polymers in aligned, coiling configurations as for example observed in plant cells. Though elasticity can account for the regularity of these arrays, it cannot account for a transverse orientation of microtubules to the cell's long axis. We therefore conclude that an additional active, force-generating process is necessary to create a coiling configuration perpendicular to the long axis of the cell.

In Operando Quantification of Three-Dimensional Water Distribution in Nanoporous Carbon-Based Layers in Polymer Electrolyte Membrane Fuel Cells.

PubMed

Alrwashdeh, Saad S; Manke, Ingo; Markötter, Henning; Klages, Merle; Göbel, Martin; Haußmann, Jan; Scholta, Joachim; Banhart, John

2017-06-27

Understanding the function of nanoporous materials employed in polymer electrolyte membrane fuel cells (PEMFCs) is crucial to improve their performance, durability, and cost efficiency. Up to now, the water distribution in the nm-sized pore structures was hardly accessible during operation of the cells. Here we demonstrate that phase contrast synchrotron X-ray tomography allows for an in operando quantification of the three-dimensional water distribution within the nm-sized pores of carbon-based microporous layers (MPLs). For this purpose, a fuel cell design optimized for tomographic phase contrast measurements was realized. Water in the pores of the entire MPL was detected and quantified. We found an inhomogeneous distribution of the local water saturation and a sharp boundary between mostly filled MPL and almost empty areas. We attribute the latter observation to the two-phase boundary created because condensation takes place predominantly on one side of the boundary. Furthermore, high water saturation in large areas hints at gas diffusion or transport along preferred three-dimensional paths through the material, therefore bypassing most of the MPL volume. Our approach may contribute significantly to future investigations of nanoporous fuel cell materials under realistic operating conditions.

3D optimization of a polymer MOEMS for active focusing of VCSEL beam

NASA Astrophysics Data System (ADS)

Abada, S.; Camps, T.; Reig, B.; Doucet, JB; Daran, E.; Bardinal, V.

2014-05-01

We report on the optimized design of a polymer-based actuator that can be directly integrated on a VCSEL for vertical beam scanning. Its operation principle is based on the vertical displacement of a SU-8 membrane including a polymer microlens. Under an applied thermal gradient, the membrane is shifted vertically due to thermal expansion in the actuation arms induced by Joule effect. This leads to a modification of microlens position and thus to a vertical scan of the laser beam. Membrane vertical displacements as high as 8μm for only 3V applied were recently experimentally obtained. To explain these performances, we developed a comprehensive tri-dimensional thermo-mechanical model that takes into account SU-8 material properties and precise MOEMS geometry. Out-of-plane mechanical coefficients and thermal conductivity were thus integrated in our 3D model (COMSOL Multiphysics). Vertical displacements extracted from these data for different actuation powers were successfully compared to experimental values, validating this modelling tool. Thereby, it was exploited to increase MOEMS electrothermal performance by a factor higher than 5.

Role of non-equilibrium conformations on driven polymer translocation

NASA Astrophysics Data System (ADS)

Katkar, H. H.; Muthukumar, M.

2018-01-01

One of the major theoretical methods in understanding polymer translocation through a nanopore is the Fokker-Planck formalism based on the assumption of quasi-equilibrium of polymer conformations. The criterion for applicability of the quasi-equilibrium approximation for polymer translocation is that the average translocation time per Kuhn segment, ⟨τ⟩/NK, is longer than the relaxation time τ0 of the polymer. Toward an understanding of conditions that would satisfy this criterion, we have performed coarse-grained three dimensional Langevin dynamics and multi-particle collision dynamics simulations. We have studied the role of initial conformations of a polyelectrolyte chain (which were artificially generated with a flow field) on the kinetics of its translocation across a nanopore under the action of an externally applied transmembrane voltage V (in the absence of the initial flow field). Stretched (out-of-equilibrium) polyelectrolyte chain conformations are deliberately and systematically generated and used as initial conformations in translocation simulations. Independent simulations are performed to study the relaxation behavior of these stretched chains, and a comparison is made between the relaxation time scale and the mean translocation time (⟨τ⟩). For such artificially stretched initial states, ⟨τ⟩/NK < τ0, demonstrating the inapplicability of the quasi-equilibrium approximation. Nevertheless, we observe a scaling of ⟨τ⟩ ˜ 1/V over the entire range of chain stretching studied, in agreement with the predictions of the Fokker-Planck model. On the other hand, for realistic situations where the initial artificially imposed flow field is absent, a comparison of experimental data reported in the literature with the theory of polyelectrolyte dynamics reveals that the Zimm relaxation time (τZimm) is shorter than the mean translocation time for several polymers including single stranded DNA (ssDNA), double stranded DNA (dsDNA), and synthetic polymers. Even when these data are rescaled assuming a constant effective velocity of translocation, it is found that for flexible (ssDNA and synthetic) polymers with NK Kuhn segments, the condition ⟨τ⟩/NK < τZimm is satisfied. We predict that for flexible polymers such as ssDNA, a crossover from quasi-equilibrium to non-equilibrium behavior would occur at NK ˜ O(1000).

Molecular engineering of chiral colloidal liquid crystals using DNA origami

NASA Astrophysics Data System (ADS)

Siavashpouri, Mahsa; Wachauf, Christian H.; Zakhary, Mark J.; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

2017-08-01

Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

Molecular engineering of chiral colloidal liquid crystals using DNA origami.

PubMed

Siavashpouri, Mahsa; Wachauf, Christian H; Zakhary, Mark J; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

2017-08-01

Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

Metal-Organic Framework-Polymer Composite as a Highly Efficient Sorbent for Sulfonamide Adsorption and Desorption: Effect of Coordinatively Unsaturated Metal Site and Topology.

PubMed

Shih, Yung-Han; Wang, Kuen-Yun; Singco, Brenda; Lin, Chia-Her; Huang, Hsi-Ya

2016-11-08

In this study, we first demonstrated the effect of two types of metal-organic framework-polymer (MOF-polymer) monoliths on in-tube solid-phase microextraction (IT-SPME) of sulfonamides. Sulfonamides were successfully adsorbed onto MIL-101(Cr)-polymer but were difficult to elute due to these sulfonamides could interact via Lewis acid-base interaction with the presence of Cr(III) coordinatively unsaturated metal sites (CUS). Moreover, the cage-type topology of MIL-101(Cr) that could produce multiple pathways thus complicates the desorption of the test analytes from the sorbent. Contrastingly, MIL-53(Al)-polymer provided weaker Al(III) CUS, and its one-dimensional channel pore structure could provide an unhindered pathway for sulfonamides transfer during elution. After optimizing the IT-SPME condition such as MOF content, pH of sample matrix, column length, extraction flow rate, and elution volume, the calculated extraction recovery of sulfonamides in MIL-53(Al)-polymer as analyzed by microemulsion electrokinetic chromatography (MEEKC) were in the range of 40%-90% with relative standard deviations (RSDs) below 5% and a reusability of at least 30 times.

Room temperature synthesis of a Zn(II) metal-organic coordination polymer for dye removal

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

Abbasi, Alireza, E-mail: aabbasi@khayam.ut.ac.ir; Gharib, Maniya; Najafi, Mahnaz

2016-03-15

A new one-dimensional (1D) coordination polymer, [Zn(4,4′-bpy)(H{sub 2}O){sub 4}](ADC)·4H{sub 2}O (1) (4,4′-bpy=4,4′-bipyridine and H{sub 2}ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at leastmore » three cycles. - Graphical abstract: A new 1D coordination polymer as catalyst for the degradation of Bismarck brown aqueous solution. - Highlights: • A 1D coordination polymer has been synthesized at room temperature. • The prepared compound was utilized for color removal of Bismarck brown dye. • Good catalytic activity and stability in the dye decolorization has been found.« less

Gravity-Driven Thin Film Flow of an Ellis Fluid.

PubMed

Kheyfets, Vitaly O; Kieweg, Sarah L

2013-12-01

The thin film lubrication approximation has been studied extensively for moving contact lines of Newtonian fluids. However, many industrial and biological applications of the thin film equation involve shear-thinning fluids, which often also exhibit a Newtonian plateau at low shear. This study presents new numerical simulations of the three-dimensional (i.e. two-dimensional spreading), constant-volume, gravity-driven, free surface flow of an Ellis fluid. The numerical solution was validated with a new similarity solution, compared to previous experiments, and then used in a parametric study. The parametric study centered around rheological data for an example biological application of thin film flow: topical drug delivery of anti-HIV microbicide formulations, e.g. hydroxyethylcellulose (HEC) polymer solutions. The parametric study evaluated how spreading length and front velocity saturation depend on Ellis parameters. A lower concentration polymer solution with smaller zero shear viscosity ( η 0 ), τ 1/2 , and λ values spread further. However, when comparing any two fluids with any possible combinations of Ellis parameters, the impact of changing one parameter on spreading length depends on the direction and magnitude of changes in the other two parameters. In addition, the isolated effect of the shear-thinning parameter, λ , on the front velocity saturation depended on τ 1/2 . This study highlighted the relative effects of the individual Ellis parameters, and showed that the shear rates in this flow were in both the shear-thinning and plateau regions of rheological behavior, emphasizing the importance of characterizing the full range of shear-rates in rheological measurements. The validated numerical model and parametric study provides a useful tool for future steps to optimize flow of a fluid with rheological behavior well-described by the Ellis constitutive model, in a range of industrial and biological applications.

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.

Tunable Optical Polymer Systems (TOPS)

DTIC Science & Technology

2001-05-01

pixelation o1 displays is done. One team member has combined this work with self-assembling layers so that it is possible to make three-dimensional...I THERMOCHROMISM I ELECTROCHEMILUMINESCENCE (ECL) I MAGNETOCHROMISM I TUNABLE ELECTROLUMINESCENCE (EL) PROTONIC BAND GAP (PBG) SELECTIVE...via Selective Reflection • Chiral-nematic liquid crystalline film as a helical stack of quasinematic layers , illustrated below with a LH structure

Structure and electrical properties of a one-dimensional polymeric silver thiosaccharinate complex with argentophilic interactions.

PubMed

Dennehy, Mariana; Amo-Ochoa, Pilar; Freire, Eleonora; Suárez, Sebastián; Halac, Emilia; Baggio, Ricardo

2018-02-01

Among the potential applications of coordination polymers, electrical conductivity ranks high in technological interest. We report the synthesis, crystal structure and spectroscopic analysis of an Ag I -thiosaccharinate one-dimensional coordination polymer {systematic name: catena-poly[[[aquatetrakis(μ 3 -1,1-dioxo-1,2-benzisothiazole-3-thiolato-κ 3 N:S 3 :S 3 )tetrasilver(I)]-μ 2 -4,4'-(propane-1,3-diyl)dipyridine-κ 2 N:N'] dimethyl sulfoxide hemisolvate]}, {[Ag 4 (C 7 H 4 NO 2 S 2 ) 4 (C 13 H 14 N 2 )(H 2 O)]·0.5C 2 H 6 OS} n , with the 4,4'-(propane-1,3-diyl)dipyridine ligand acting as a spacer. A relevant feature of the structure is the presence of an unusually short Ag...Ag distance of 2.8306 (9) Å, well within the range of argentophilic interactions, confirmed experimentally as such by a Raman study on the low-frequency spectrum, and corroborated theoretically by an Atoms in Molecules (AIM) analysis of the calculated electron density. Electrical conductivity measurements show that this complex can act as a semiconductor with moderate conductivity.

2D mesoscale colloidal crystal patterns on polymer substrates

NASA Astrophysics Data System (ADS)

Bredikhin, Vladimir; Bityurin, Nikita

2018-05-01

The development of nanosphere lithography relies on the ability of depositing 2D colloidal crystals comprising micro- and nano-size elements on substrates of different materials. One of the most difficult problems here is deposition of coatings on hydrophobic substrates, e.g. polymers, from aqueous colloidal solutions. We use UV photooxidation for substrate hydrophilization. We demonstrate a new method of producing a two-dimensional ordered array of polymer microparticles (polystyrene microspheres ∼1 μm in diameter) on a polymer substrate (PMMA). We show that implementation of the new deposition technique for directed self-assembly of microspheres on an UV irradiated surface provides an opportunity to obtain coatings on a hydrophilized PMMA surface of large area (∼5 cm2). UV irradiation of the surface through masks allows creating 2D patterns consisting of mesoscale elements formed by the deposited self-assembled microparticles owing to the fact that the colloidal particles are deposited only on the irradiated area leaving the non-irradiated sections intact.

Interpenetrating and non-interpenetrating 3-dimensional coordination polymer frameworks from multiple building blocks

NASA Astrophysics Data System (ADS)

Bradshaw, Darren; Rosseinsky, Matthew J.

2005-12-01

Reaction of Co(NO3)2ṡ6H2O with the multidentate ligands benzene-1,3,5-tricarboxylate (btc) and the flexible bipyridyl ligand 1,2-bis(4-pyridyl)ethane (bpe) affords the 3-dimensional coordination polymers [Co3(btc)2(bpe)3(eg)2]ṡ(guests) 1, where eg = ethylene glycol, and [Co2(Hbtc)2(bpe)2]ṡ(bpe) 2. Both phases are comprised of infinite metal-carboxylate dimer chains, linked into 2-dimensional sheets by the bpe ligands. These sheets are further linked to adjacent sheets through covalent interactions, 1, or through hydrogen-bonding interactions, 2, to yield the 3-dimensional structures. Phase 1 exhibits solvent filled 1-dimensional pores, whereas 2 is triply-interpenetrated to form a dense solid array.

Monte Carlo Technique Used to Model the Degradation of Internal Spacecraft Surfaces by Atomic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Miller, Sharon K.

2004-01-01

Atomic oxygen is one of the predominant constituents of Earth's upper atmosphere. It is created by the photodissociation of molecular oxygen (O2) into single O atoms by ultraviolet radiation. It is chemically very reactive because a single O atom readily combines with another O atom or with other atoms or molecules that can form a stable oxide. The effects of atomic oxygen on the external surfaces of spacecraft in low Earth orbit can have dire consequences for spacecraft life, and this is a well-known and much studied problem. Much less information is known about the effects of atomic oxygen on the internal surfaces of spacecraft. This degradation can occur when openings in components of the spacecraft exterior exist that allow the entry of atomic oxygen into regions that may not have direct atomic oxygen attack but rather scattered attack. Openings can exist because of spacecraft venting, microwave cavities, and apertures for Earth viewing, Sun sensors, or star trackers. The effects of atomic oxygen erosion of polymers interior to an aperture on a spacecraft were simulated at the NASA Glenn Research Center by using Monte Carlo computational techniques. A two-dimensional model was used to provide quantitative indications of the attenuation of atomic oxygen flux as a function of the distance into a parallel-walled cavity. The model allows the atomic oxygen arrival direction, the Maxwell Boltzman temperature, and the ram energy to be varied along with the interaction parameters of the degree of recombination upon impact with polymer or nonreactive surfaces, the initial reaction probability, the reaction probability dependence upon energy and angle of attack, degree of specularity of scattering of reactive and nonreactive surfaces, and the degree of thermal accommodation upon impact with reactive and non-reactive surfaces to be varied to allow the model to produce atomic oxygen erosion geometries that replicate actual experimental results from space. The degree of erosion of various interior locations was compared with the erosion that would occur external to the spacecraft. Results of one cavity model indicate that, at depths into a two-dimensional cavity that are equal to 10 cavity widths, the erosion on the walls of the cavity is less than that on the top surface by over 2 orders of magnitude. Wall erosion near the surface of a cavity depends on which wall is receiving direct atomic oxygen attack. However, deep in the cavity little difference is present. Testing of various cavity models such as these gives spacecraft designers an indication of the level of threat to sensitive interior surfaces for different geometries. Even though the Monte Carlo model is two-dimensional, it can be used to provide qualitative information about spacecraft openings that are three-dimensional by offering reasonable insight as to the nature of the attenuation of damage that occurs within a spacecraft in low Earth orbit. As shown, there is more erosion on the side seeing direct atomic oxygen attack until a depth of approximately 5 times the width of the opening, where the erosion is the same on both sides.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Rheological and fractal characteristics of unconditioned and conditioned water treatment residuals.

PubMed

Dong, Y J; Wang, Y L; Feng, J

2011-07-01

The rheological and fractal characteristics of raw (unconditioned) and conditioned water treatment residuals (WTRs) were investigated in this study. Variations in morphology, size, and image fractal dimensions of the flocs/aggregates in these WTR systems with increasing polymer doses were analyzed. The results showed that when the raw WTRs were conditioned with the polymer CZ8688, the optimum polymer dosage was observed at 24 kg/ton dry sludge. The average diameter of irregularly shaped flocs/aggregates in the WTR suspensions increased from 42.54 μm to several hundred micrometers with increasing polymer doses. Furthermore, the aggregates in the conditioned WTR system displayed boundary/surface and mass fractals. At the optimum polymer dosage, the aggregates formed had a volumetric average diameter of about 820.7 μm, with a one-dimensional fractal dimension of 1.01 and a mass fractal dimension of 2.74 on the basis of the image analysis. Rheological tests indicated that the conditioned WTRs at the optimum polymer dosage showed higher levels of shear-thinning behavior than the raw WTRs. Variations in the limiting viscosity (η(∞)) of conditioned WTRs with sludge content could be described by a linear equation, which were different from the often-observed empirical exponential relationship for most municipal sludge. With increasing temperature, the η(∞) of the raw WTRs decreased more rapidly than that of the raw WTRs. Good fitting results for the relationships between lgη(∞)∼T using the Arrhenius equation indicate that the WTRs had a much higher activation energy for viscosity of about 17.86-26.91 J/mol compared with that of anaerobic granular sludge (2.51 J/mol) (Mu and Yu, 2006). In addition, the Bingham plastic model adequately described the rheological behavior of the conditioned WTRs, whereas the rheology of the raw WTRs fit the Herschel-Bulkley model well at only certain sludge contents. Considering the good power-law relationships between the limiting viscosity and sludge content of the conditioned WTRs, their mass fractal dimensions were calculated through the models proposed by Shih et al. (1990), which were 2.48 for these conditioned WTR aggregates. The results demonstrate that conditioned WTRs behave like weak-link flocs/aggregates. Copyright © 2011 Elsevier Ltd. All rights reserved.

Development of a Three-Dimensional, Unstructured Material Response Design Tool

NASA Technical Reports Server (NTRS)

Schulz, Joseph C.; Stern, Eric C.; Muppidi, Suman; Palmer, Grant E.; Schroeder, Olivia

2017-01-01

A preliminary verification and validation of a new material response model is presented. This model, Icarus, is intended to serve as a design tool for the thermal protection systems of re-entry vehicles. Currently, the capability of the model is limited to simulating the pyrolysis of a material as a result of the radiative and convective surface heating imposed on the material from the surrounding high enthalpy gas. Since the major focus behind the development of Icarus has been model extensibility, the hope is that additional physics can be quickly added. This extensibility is critical since thermal protection systems are becoming increasing complex, e.g. woven carbon polymers. Additionally, as a three-dimensional, unstructured, finite-volume model, Icarus is capable of modeling complex geometries. In this paper, the mathematical and numerical formulation is presented followed by a discussion of the software architecture and some preliminary verification and validation studies.

On compression and damage evolution in two thermoplastics

PubMed Central

Garcea, S. C.; Eastwood, D. S.; Parry, S.; Rau, C.; Withers, P. J.; McDonald, S. A.; Brown, E. N.

2017-01-01

The well-known Taylor cylinder impact test, which follows the impact of a flat-ended cylindrical rod onto a rigid stationary anvil, is conducted over a range of impact speeds for two polymers, polytetrafluoroethylene (PTFE) and polyetheretherketone (PEEK). In previous work, experiments and a model were developed to capture the deformation behaviour of the cylinder after impact. These works showed a region in which spatial and temporal variation of both longitudinal and radial deformation provided evidence of changes in phase within the material. In this further series of experiments, this region is imaged in a range of impacted targets at the Diamond synchrotron. Further techniques were fielded to resolve compressed regions within the recovered polymer cylinders that showed a fracture zone in the impact region. The combination of macroscopic high-speed photography and three-dimensional X-ray imaging has identified the development of failure with these polymers and shown that there is no abrupt transition in behaviours but rather a continuous range of responses to competing operating mechanisms. The behaviours noted in PEEK in these polymers show critical gaps in understanding of polymer high strain-rate response. PMID:28265185

Molecular structure of dextran sulphate sodium in aqueous environment

NASA Astrophysics Data System (ADS)

Yu, Miao; Every, Hayley A.; Jiskoot, Wim; Witkamp, Geert-Jan; Buijs, Wim

2018-03-01

Here we propose a 3D-molecular structural model for dextran sulphate sodium (DSS) in a neutral aqueous environment based on the results of a molecular modelling study. The DSS structure is dominated by the stereochemistry of the 1,6-linked α-glucose units and the presence of two sulphate groups on each α-glucose unit. The structure of DSS can be best described as a helix with various patterns of di-sulphate substitution on the glucose rings. The presence of a side chain does not alter the 3D-structure of the linear main chain much, but affects the overall spatial dimension of the polymer. The simulated polymers have a diameter similar to or in some cases even larger than model α-hemolysin nano-pores for macromolecule transport in many biological processes, indicating a size-limited translocation through such pores. All results of the molecular modelling study are in line with previously reported experimental data. This study establishes the three-dimensional structure of DSS and summarizes the spatial dimension of the polymer, serving as the basis for a better understanding on the molecular level of DSS-involved electrostatic interaction processes with biological components like proteins and cell pores.

Constitutive Modeling of Nanotube-Reinforced Polymer Composite Systems

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Harik, Vasyl M.; Wise, Kristopher E.; Gates, Thomas S.

2004-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT). Since the polymer molecules are on the same size scale as the nanotubes, the interaction at the polymer/nanotube interface is highly dependent on the local molecular structure and bonding. At these small length scales, the lattice structures of the nanotube and polymer chains cannot be considered continuous, and the bulk mechanical properties of the SWNT/polymer composites can no longer be determined through traditional micromechanical approaches that are formulated using continuum mechanics. It is proposed herein that the nanotube, the local polymer near the nanotube, and the nanotube/polymer interface can be modeled as an effective continuum fiber using an equivalent-continuum modeling method. The effective fiber retains the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composites with various nanotube sizes and orientations. As an example, the proposed approach is used for the constitutive modeling of two SWNT/polyethylene composite systems, one with continuous and aligned SWNT and the other with discontinuous and randomly aligned nanotubes.

Constitutive Modeling of Nanotube-Reinforced Polymer Composite Systems

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Harik, Vasyl M.; Wise, Kristopher E.; Gates, Thomas S.

2001-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT). Since the polymer molecules are on the same size scale as the nanotubes, the interaction at the polymer/nanotube interface is highly dependent on the local molecular structure and bonding. At these small length scales, the lattice structures of the nanotube and polymer chains cannot be considered continuous, and the bulk mechanical properties of the SWNT/polymer composites can no longer be determined through traditional micromechanical approaches that are formulated using continuum mechanics. It is proposed herein that the nanotube, the local polymer near the nanotube, and the nanotube/polymer interface can be modeled as an effective continuum fiber using an equivalent-continuum modeling method. The effective fiber retains the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composites with various nanotube sizes and orientations. As an example, the proposed approach is used for the constitutive modeling of two SWNT/polyethylene composite systems, one with continuous and aligned SWNT and the other with discontinuous and randomly aligned nanotubes.

Non-monotonic course of protein solubility in aqueous polymer-salt solutions can be modeled using the sol-mxDLVO model.

PubMed

Herhut, Marcel; Brandenbusch, Christoph; Sadowski, Gabriele

2016-02-01

Protein purification is often performed using cost-intensive chromatographic steps. To discover economic alternatives (e.g., crystallization), knowledge on protein solubility as a function of temperature, pH, and additives in solution as well as their concentration is required. State-of-the-art models for predicting protein solubility almost exclusively consider aqueous salt systems, whereas "salting-in" and "salting-out" effects induced by the presence of an additional polymer are not considered. Thus, we developed the sol-mxDLVO model. Using this newly developed model, protein solubility in the presence of one salt and one polymer, especially the non-monotonic course of protein solubility, could be predicted. Systems considered included salts (NaCl, Na-p-Ts, (NH(4))(2) SO(4)) and the polymer polyethylene glycol (MW: 2000 g/mol, 12000 g/mol) and proteins lysozyme from chicken egg white (pH 4 to 5.5) and D-xylose ketol-isomerase (pH 7) at 298.15 K. The results show that by using the sol-mxDLVO model, protein solubility in polymer-salt solutions can be modeled in good agreement with the experimental data for both proteins considered. The sol-mxDLVO model can describe the non-monotonic course of protein solubility as a function of polymer concentration and salt concentration, previously not covered by state-of-the-art models. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of damage-softened material behavior in the fracture of composites and adhesives

NASA Technical Reports Server (NTRS)

Ungsuwarungsri, T.; Knauss, W. G.

1986-01-01

Failure mechanisms of materials under very high strains experienced at and ahead of the crack tip such as formation, growth, and interaction of microvoids in ductile materials, microcracks in brittle solids or crazes in polymers and adhesives are represented by one-dimensional, nonlinear stress-strain relations possessing different ways by which the material loses capacity to carry load up to fracture or total separation. A double cantilever beam (DCB) type specimen is considered. The nonlinear material is confined to a thin strip between the two elastic beams loaded by a wedge. The problem is first modeled as a beam on a nonlinear foundation. The pertinent equation is solved numerically as a two-point boundary value problem for both the stationary and the quasi-stationay propagating crack. A finite element model is then used to model the problem in more detail in order to assess the adequacy of the beam model for the reduction of experimental data to determine in-situ properties of the thin interlayer.

Dual exposure, two-photon, conformal phasemask lithography for three dimensional silicon inverse woodpile photonic crystals

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

Shir, Daniel J.; Nelson, Erik C.; Chanda, Debashis

2010-01-01

The authors describe the fabrication and characterization of three dimensional silicon inverse woodpile photonic crystals. A dual exposure, two-photon, conformal phasemask technique is used to create high quality polymer woodpile structures over large areas with geometries that quantitatively match expectations based on optical simulations. Depositing silicon into these templates followed by the removal of the polymer results in silicon inverse woodpile photonic crystals for which calculations indicate a wide, complete photonic bandgap over a range of structural fill fractions. Spectroscopic measurements of normal incidence reflection from both the polymer and siliconphotonic crystals reveal good optical properties.

Crystal structure and charge transport properties of poly(arylene-ethynylene) derivatives: A DFT approach

NASA Astrophysics Data System (ADS)

Garzón, Andrés; Granadino-Roldán, José M.; García, Gregorio; Moral, Mónica; Fernández-Gómez, Manuel

2013-04-01

In the present study, a series of crystalline poly(arylene-ethynylene) copolymers containing phenylethynylene and 2,5-dialkoxy-phenylethynylene units together with 1,3,4-thiadiazole rings has been modeled by means of periodic calculations. Optimized three-dimensional polymeric structures show interchain distances that are consistent with the experimental values reported for a related polymer. It has also been observed that the presence of pendant alkoxy chains brings on both a further flattening and a separation of the coplanar chains. This fact is linked to a decrease of the interchain cofacial distance. The electron transport character of the polymer crystal structures was assessed through Marcus theory. Electronic coupling between neighboring polymer chains is most influenced by the presence of alkoxy chains giving rise to an expectable enhancement of the electron hopping mobility.

Additive Manufacturing of Metallic and Ceramic Components by the Material Extrusion of Highly-Filled Polymers: A Review and Future Perspectives

PubMed Central

Cano, Santiago

2018-01-01

Additive manufacturing (AM) is the fabrication of real three-dimensional objects from metals, ceramics, or plastics by adding material, usually as layers. There are several variants of AM; among them material extrusion (ME) is one of the most versatile and widely used. In MEAM, molten or viscous materials are pushed through an orifice and are selectively deposited as strands to form stacked layers and subsequently a three-dimensional object. The commonly used materials for MEAM are thermoplastic polymers and particulate composites; however, recently innovative formulations of highly-filled polymers (HP) with metals or ceramics have also been made available. MEAM with HP is an indirect process, which uses sacrificial polymeric binders to shape metallic and ceramic components. After removing the binder, the powder particles are fused together in a conventional sintering step. In this review the different types of MEAM techniques and relevant industrial approaches for the fabrication of metallic and ceramic components are described. The composition of certain HP binder systems and powders are presented; the methods of compounding and filament making HP are explained; the stages of shaping, debinding, and sintering are discussed; and finally a comparison of the parts produced via MEAM-HP with those produced via other manufacturing techniques is presented. PMID:29783705

Additive Manufacturing of Metallic and Ceramic Components by the Material Extrusion of Highly-Filled Polymers: A Review and Future Perspectives.

PubMed

Gonzalez-Gutierrez, Joamin; Cano, Santiago; Schuschnigg, Stephan; Kukla, Christian; Sapkota, Janak; Holzer, Clemens

2018-05-18

Additive manufacturing (AM) is the fabrication of real three-dimensional objects from metals, ceramics, or plastics by adding material, usually as layers. There are several variants of AM; among them material extrusion (ME) is one of the most versatile and widely used. In MEAM, molten or viscous materials are pushed through an orifice and are selectively deposited as strands to form stacked layers and subsequently a three-dimensional object. The commonly used materials for MEAM are thermoplastic polymers and particulate composites; however, recently innovative formulations of highly-filled polymers (HP) with metals or ceramics have also been made available. MEAM with HP is an indirect process, which uses sacrificial polymeric binders to shape metallic and ceramic components. After removing the binder, the powder particles are fused together in a conventional sintering step. In this review the different types of MEAM techniques and relevant industrial approaches for the fabrication of metallic and ceramic components are described. The composition of certain HP binder systems and powders are presented; the methods of compounding and filament making HP are explained; the stages of shaping, debinding, and sintering are discussed; and finally a comparison of the parts produced via MEAM-HP with those produced via other manufacturing techniques is presented.

Organosilicon Polymers as Precursors for Silicon Containing Ceramics: Recent Developments.

DTIC Science & Technology

1987-08-14

the polymer to a ceramic material, hopefully of the desired composition . In the latter alternative, shrinkage during pyrolysis should not be great...carbon-carbon composite materials. In order to have a useful preceramic polymer . considerations of structure and reactivitv are of paramount importance...process so that on pyrolysis non-volatile, three-dimensional networks (which lead to maximum weight retention) are formed. Thus. preceramic polymer

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media

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

Kumar, Rajeev

2017-02-14

Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes frommore » the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.« less

Manufacturing a Porous Structure According to the Process Parameters of Functional 3D Porous Polymer Printing Technology Based on a Chemical Blowing Agent

NASA Astrophysics Data System (ADS)

Yoo, C. J.; Shin, B. S.; Kang, B. S.; Yun, D. H.; You, D. B.; Hong, S. M.

2017-09-01

In this paper, we propose a new porous polymer printing technology based on CBA(chemical blowing agent), and describe the optimization process according to the process parameters. By mixing polypropylene (PP) and CBA, a hybrid CBA filament was manufactured; the diameter of the filament ranged between 1.60 mm and 1.75 mm. A porous polymer structure was manufactured based on the traditional fused deposition modelling (FDM) method. The process parameters of the three-dimensional (3D) porous polymer printing (PPP) process included nozzle temperature, printing speed, and CBA density. Porosity increase with an increase in nozzle temperature and CBA density. On the contrary, porosity increase with a decrease in the printing speed. For porous structures, it has excellent mechanical properties. We manufactured a simple shape in 3D using 3D PPP technology. In the future, we will study the excellent mechanical properties of 3D PPP technology and apply them to various safety fields.

Electroless Deposition of Palladium on Macroscopic 3D-Printed Polymers with Dense Microlattice Architectures for Development of Multifunctional Composite Materials

DOE PAGES

Jones, Christopher G.; Mills, Bernice E.; Nishimoto, Ryan K.; ...

2017-10-25

A simple procedure has been developed to create palladium (Pd) films on the surface of several common polymers used in commercial fused deposition modeling (FDM) and stereolithography (SLA) based three-dimensional (3D) printing by an electroless deposition process. The procedure can be performed at room temperature, with equipment less expensive than many 3D printers, and occurs rapidly enough to achieve full coverage of the film within a few minutes. 3D substrates composed of dense logpile or cubic lattices with part sizes in the mm to cm range, and feature sizes as small as 150 μm were designed and printed using commerciallymore » available 3D printers. The deposition procedure was successfully adapted to show full coverage in the lattice substrates. As a result, the ability to design, print, and metallize highly ordered three-dimensional microscale structures could accelerate development of a range of optimized chemical and mechanical engineering systems.« less

Electroless Deposition of Palladium on Macroscopic 3D-Printed Polymers with Dense Microlattice Architectures for Development of Multifunctional Composite Materials

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

Jones, Christopher G.; Mills, Bernice E.; Nishimoto, Ryan K.

A simple procedure has been developed to create palladium (Pd) films on the surface of several common polymers used in commercial fused deposition modeling (FDM) and stereolithography (SLA) based three-dimensional (3D) printing by an electroless deposition process. The procedure can be performed at room temperature, with equipment less expensive than many 3D printers, and occurs rapidly enough to achieve full coverage of the film within a few minutes. 3D substrates composed of dense logpile or cubic lattices with part sizes in the mm to cm range, and feature sizes as small as 150 μm were designed and printed using commerciallymore » available 3D printers. The deposition procedure was successfully adapted to show full coverage in the lattice substrates. As a result, the ability to design, print, and metallize highly ordered three-dimensional microscale structures could accelerate development of a range of optimized chemical and mechanical engineering systems.« less

Stability of the sectored morphology of polymer crystallites

NASA Astrophysics Data System (ADS)

Alageshan, Jaya Kumar; Hatwalne, Yashodhan; Muthukumar, Murugappan

2016-09-01

When an entangled interpenetrating collection of long flexible polymer chains dispersed in a suitable solvent is cooled to low enough temperatures, thin lamellar crystals form. Remarkably, these lamellae are sectored, with several growth sectors that have differing melting temperatures and growth kinetics, eluding so far an understanding of their origins. We present a theoretical model to explain this six-decade-old challenge by addressing the elasticity of fold surfaces of finite-sized lamella in the presence of disclination-type topological defects arising from anisotropic line tension. Entrapment of a disclination defect in a lamella results in sectors separated by walls, which are soliton solutions of a two-dimensional elliptic sine-Gordon equation. For flat square morphologies, exact results show that sectored squares are more stable than plain squares if the dimensionless anisotropic line tension parameter α =γa n/√{h4Kϕ } (γa n = anisotropic line tension, h4 = fold energy parameter, Kϕ = elastic constant for two-dimensional orientational deformation) is above a critical value, which depends on the size of the square.

Supramolecular architectures in Co(II) and Cu(II) complexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands.

PubMed

Karthikeyan, Ammasai; Thomas Muthiah, Packianathan; Perdih, Franc

2016-05-01

The coordination chemistry of mixed-ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal-organic framworks are emerging as novel functional materials. Aminopyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic-inorganic hybrid materials and coordination polymers. Thiophenecarboxylic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thiophenecarboxylate have many biological applications, for example, as antifungal and antitumor agents. Two new cobalt(II) and copper(II) complexes incorporating thiophene-2-carboxylate (2-TPC) and 2-amino-4,6-dimethoxypyrimidine (OMP) ligands have been synthesized and characterized by X-ray diffraction studies, namely (2-amino-4,6-dimethoxypyrimidine-κN)aquachlorido(thiophene-2-carboxylato-κO)cobalt(II) monohydrate, [Co(C5H3O2S)Cl(C6H9N3O2)(H2O)]·H2O, (I), and catena-poly[copper(II)-tetrakis(μ-thiophene-2-carboxylato-κ(2)O:O')-copper(II)-(μ-2-amino-4,6-dimethoxypyrimidine-κ(2)N(1):N(3))], [Cu2(C5H3O2S)4(C6H9N3O2)]n, (II). In (I), the Co(II) ion has a distorted tetrahedral coordination environment involving one O atom from a monodentate 2-TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water molecule. An additional water molecule is present in the asymmetric unit. The amino group of the coordinated OMP molecule and the coordinated carboxylate O atom of the 2-TPC ligand form an interligand N-H...O hydrogen bond, generating an S(6) ring motif. The pyrimidine molecules also form a base pair [R2(2)(8) motif] via a pair of N-H...N hydrogen bonds. These interactions, together with O-H...O and O-H...Cl hydrogen bonds and π-π stacking interactions, generate a three-dimensional supramolecular architecture. The one-dimensional coordination polymer (II) contains the classical paddle-wheel [Cu2(CH3COO)4(H2O)2] unit, where each carboxylate group of four 2-TPC ligands bridges two square-pyramidally coordinated Cu(II) ions and the apically coordinated OMP ligands bridge the dinuclear copper units. Each dinuclear copper unit has a crystallographic inversion centre, whereas the bridging OMP ligand has crystallographic twofold symmetry. The one-dimensional polymeric chains self-assemble via N-H...O, π-π and C-H...π interactions, generating a three-dimensional supramolecular architecture.

Three-dimensional dose verification of the clinical application of gamma knife stereotactic radiosurgery using polymer gel and MRI.

PubMed

Papagiannis, P; Karaiskos, P; Kozicki, M; Rosiak, J M; Sakelliou, L; Sandilos, P; Seimenis, I; Torrens, M

2005-05-07

This work seeks to verify multi-shot clinical applications of stereotactic radiosurgery with a Leksell Gamma Knife model C unit employing a polymer gel-MRI based experimental procedure, which has already been shown to be capable of verifying the precision and accuracy of dose delivery in single-shot gamma knife applications. The treatment plan studied in the present work resembles a clinical treatment case of pituitary adenoma using four 8 mm and one 14 mm collimator helmet shots to deliver a prescription dose of 15 Gy to the 50% isodose line (30 Gy maximum dose). For the experimental dose verification of the treatment plan, the same criteria as those used in the clinical treatment planning evaluation were employed. These included comparison of measured and GammaPlan calculated data, in terms of percentage isodose contours on axial, coronal and sagittal planes, as well as 3D plan evaluation criteria such as dose-volume histograms for the target volume, target coverage and conformity indices. Measured percentage isodose contours compared favourably with calculated ones despite individual point fluctuations at low dose contours (e.g., 20%) mainly due to the effect of T2 measurement uncertainty on dose resolution. Dose-volume histogram data were also found in a good agreement while the experimental results for the percentage target coverage and conformity index were 94% and 1.17 relative to corresponding GammaPlan calculations of 96% and 1.12, respectively. Overall, polymer gel results verified the planned dose distribution within experimental uncertainties and uncertainty related to the digitization process of selected GammaPlan output data.

Sacrificial bonds and hidden length in biomaterials: A kinetic constitutive description of strength and toughness in bone

NASA Astrophysics Data System (ADS)

Lieou, Charles K. C.; Elbanna, Ahmed E.; Carlson, Jean M.

2013-07-01

Sacrificial bonds and hidden length in structural molecules account for the greatly increased fracture toughness of biological materials compared to synthetic materials without such structural features by providing a molecular-scale mechanism for energy dissipation. One example is in the polymeric glue connection between collagen fibrils in animal bone. In this paper we propose a simple kinetic model that describes the breakage of sacrificial bonds and the release of hidden length, based on Bell's theory. We postulate a master equation governing the rates of bond breakage and formation. This enables us to predict the mechanical behavior of a quasi-one-dimensional ensemble of polymers at different stretching rates. We find that both the rupture peak heights and maximum stretching distance increase with the stretching rate. In addition, our theory naturally permits the possibility of self-healing in such biological structures.

Two-dimensional magnesium oxide nanosheets reinforced epoxy nanocomposites for enhanced fracture toughness

NASA Astrophysics Data System (ADS)

Balguri, Praveen Kumar; Harris Samuel, D. G.; Guruvishnu, T.; Aditya, D. B.; Mahadevan, S. M.; Thumu, Udayabhaskararao

2018-01-01

Metal oxide nanoparticles have been used as excellent reinforcements to enhance mechanical properties of polymers, natural composites, and ceramics. To date, a major portion of metal oxides used as nanofillers is three dimensional spherical nanoparticles. In the last decade, two-dimensional (2D) materials such as graphene have been widely investigated to improve the mechanical and electrical properties of polymer materials. In this paper, 2D Magnesium oxide (MgO) nanosheets reinforced epoxy composites (0.1, 0.2 and 0.4 wt%) are fabricated and studied for their ability to resist the propagation of preexisting flaw by conducting fracture toughness test for K IC, critical stress intensity factor. This property is an important mechanical property for designing applications in various engineering technologies. Our results show that the MgO with 0.2 wt% is the optimized level to improve the fracture toughness of the epoxy polymer by 47%.

Investigation of the binding properties of a multi-modular GH45 cellulase using bioinspired model assemblies.

PubMed

Fong, Monica; Berrin, Jean-Guy; Paës, Gabriel

2016-01-01

Enzymes degrading plant biomass polymers are widely used in biotechnological applications. Their efficiency can be limited by non-specific interactions occurring with some chemical motifs. In particular, the lignin component is known to bind enzymes irreversibly. In order to determine interactions of enzymes with their substrates, experiments are usually performed on isolated simple polymers which are not representative of plant cell wall complexity. But when using natural plant substrates, the role of individual chemical and structural features affecting enzyme-binding properties is also difficult to decipher. We have designed and used lignified model assemblies of plant cell walls as templates to characterize binding properties of multi-modular cellulases. These three-dimensional assemblies are modulated in their composition using the three principal polymers found in secondary plant cell walls (cellulose, hemicellulose, and lignin). Binding properties of enzymes are obtained from the measurement of their mobility that depends on their interactions with the polymers and chemical motifs of the assemblies. The affinity of the multi-modular GH45 cellulase was characterized using a statistical analysis to determine the role played by each assembly polymer. Presence of hemicellulose had much less impact on affinity than cellulose and model lignin. Depending on the number of CBMs appended to the cellulase catalytic core, binding properties toward cellulose and lignin were highly contrasted. Model assemblies bring new insights into the molecular determinants that are responsible for interactions between enzymes and substrate without the need of complex analysis. Consequently, we believe that model bioinspired assemblies will provide relevant information for the design and optimization of enzyme cocktails in the context of biorefineries.

Minimizers with Bounded Action for the High-Dimensional Frenkel-Kontorova Model

NASA Astrophysics Data System (ADS)

Miao, Xue-Qing; Wang, Ya-Nan; Qin, Wen-Xin

In Aubry-Mather theory for monotone twist maps or for one-dimensional Frenkel-Kontorova (FK) model with nearest neighbor interactions, each global minimizer (minimal energy configuration) is naturally Birkhoff. However, this is not true for the one-dimensional FK model with non-nearest neighbor interactions or for the high-dimensional FK model. In this paper, we study the Birkhoff property of minimizers with bounded action for the high-dimensional FK model.

Design and fabrication of thin microvascularised polymer matrices inspired from secondary lamellae of fish gills

NASA Astrophysics Data System (ADS)

Kumar, Prasoon; Gandhi, Prasanna S.; Majumder, Mainak

2016-04-01

Gills are one of the most primitive gas, solute exchange organs available in fishes. They facilitate exchange of gases, solutes and ions with a surrounding water medium through their functional unit called secondary lamella. These lamellae through their extraordinary morphometric features and peculiar arrangement in gills, achieve remarkable mass transport properties. Therefore, in the current study, modeling and simulation of convection-diffusion transport through a two dimensional model of secondary lamella and theoretical analysis of morphometric features of fish gills were carried out. Such study suggested an evolutionary conservation of parametric ratios across fishes of different weights. Further, we have also fabricated a thin microvascularised PDMS matrices mimicking secondary lamella by use of micro-technologies like electrospinning. In addition, we have also demonstrated the fluid flow by capillary action through these thin microvascularised PDMS matrices. Eventually, we also illustrated the application of these thin microvascularied PDMS matrices in solute exchange process under capillary flow conditions. Thus, our study suggested that fish gills have optimized parameteric ratios, at multiple length scale, throughout an evolution to achieve an organ with enhanced mass transport capabilities. Thus, these defined parametric ratios could be exploited to design and develop efficient, scaled-up gas/solute exchange microdevices. We also proposed an inexpensive and scalable method of fabrication of thin microvascularised polymer matrices and demonstrated its solute exchange capabilities under capillary flow conditions. Thus, mimicking the microstructures of secondary lamella will enable fabrication of microvascularised thin polymer systems through micro manufacturing technologies for potential applications in filtration, self-healing/cooling materials and bioengineering.

Two-dimensiosnal electron beam charging model for polymer films. M.S. Thesis; [spacecraft charging, geosynchronous satellites

NASA Technical Reports Server (NTRS)

Reeves, R. D.; Balmain, K. G.

1981-01-01

A two dimensional model was developed to describe the charging of thin polymer films exposed to a uniform mon-energetic electron beam. The study was motivated by observed anomalous behavior of geosynchronous satellites which was attributed to electrical discharges associated with the differential charging of satellite surfaces of magnetospheric electrons. Electric fields both internal and external to the irradiated specimen were calculated at steady state in order to identify regions of high electrical stress. Particular emphasis was placed on evaluating the charging characteristics near the material's edge. The model was used to identify and quantify the effects of some of the experimental parameters notably: beam energy; beam angle of incidence; beam current density; material thickness; and material width. Simulations of the following situations were also conducted: positive or negative precharging over part of the surface; a central gap in the material; and a discontinuity in the material's thickness.

A Fortran 90 Hartree-Fock program for one-dimensional periodic π-conjugated systems using Pariser-Parr-Pople model

NASA Astrophysics Data System (ADS)

Kondayya, Gundra; Shukla, Alok

2012-03-01

Pariser-Parr-Pople (P-P-P) model Hamiltonian is employed frequently to study the electronic structure and optical properties of π-conjugated systems. In this paper we describe a Fortran 90 computer program which uses the P-P-P model Hamiltonian to solve the Hartree-Fock (HF) equation for infinitely long, one-dimensional, periodic, π-electron systems. The code is capable of computing the band structure, as also the linear optical absorption spectrum, by using the tight-binding and the HF methods. Furthermore, using our program the user can solve the HF equation in the presence of a finite external electric field, thereby, allowing the simulation of gated systems. We apply our code to compute various properties of polymers such as trans-polyacetylene, poly- para-phenylene, and armchair and zigzag graphene nanoribbons, in the infinite length limit. Program summaryProgram title: ppp_bulk.x Catalogue identifier: AEKW_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEKW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 87 464 No. of bytes in distributed program, including test data, etc.: 2 046 933 Distribution format: tar.gz Programming language: Fortran 90 Computer: PCs and workstations Operating system: Linux, Code was developed and tested on various recent versions of 64-bit Fedora including Fedora 14 (kernel version 2.6.35.12-90). Classification: 7.3 External routines: This program needs to link with LAPACK/BLAS libraries compiled with the same compiler as the program. For the Intel Fortran Compiler we used the ACML library version 4.4.0, while for the gfortran compiler we used the libraries supplied with the Fedora distribution. Nature of problem: The electronic structure of one-dimensional periodic π-conjugated systems is an intense area of research at present because of the tremendous interest in the physics of conjugated polymers and graphene nanoribbons. The computer program described in this paper provides an efficient way of solving the Hartree-Fock equations for such systems within the P-P-P model. In addition to the Bloch orbitals, band structure, and the density of states, the program can also compute quantities such as the linear absorption spectrum, and the electro-absorption spectrum of these systems. Solution method: For a one-dimensional periodic π-conjugated system lying in the xy-plane, the single-particle Bloch orbitals are expressed as linear combinations of p-orbitals of individual atoms. Then using various parameters defining the P-P-P Hamiltonian, the Hartree-Fock equations are set up as a matrix eigenvalue problem in the k-space. Thereby, its solutions are obtained in a self-consistent manner, using the iterative diagonalizing technique at several k points. The band structure and the corresponding Bloch orbitals thus obtained are used to perform a variety of calculations such as the density of states, linear optical absorption spectrum, electro-absorption spectrum, etc. Running time: Most of the examples provided take only a few seconds to run. For a large system, however, depending on the system size, the run time may be a few minutes to a few hours.

Radiation Shielding Systems Using Nanotechnology

NASA Technical Reports Server (NTRS)

Chen, Bin (Inventor); McKay, Christoper P. (Inventor)

2011-01-01

A system for shielding personnel and/or equipment from radiation particles. In one embodiment, a first substrate is connected to a first array or perpendicularly oriented metal-like fingers, and a second, electrically conducting substrate has an array of carbon nanostructure (CNS) fingers, coated with an electro-active polymer extending toward, but spaced apart from, the first substrate fingers. An electric current and electric charge discharge and dissipation system, connected to the second substrate, receives a current and/or voltage pulse initially generated when the first substrate receives incident radiation. In another embodiment, an array of CNSs is immersed in a first layer of hydrogen-rich polymers and in a second layer of metal-like material. In another embodiment, a one- or two-dimensional assembly of fibers containing CNSs embedded in a metal-like matrix serves as a radiation-protective fabric or body covering.

In situ monitoring of laser-induced periodic surface structures formation on polymer films by grazing incidence small-angle X-ray scattering.

PubMed

Rebollar, Esther; Rueda, Daniel R; Martín-Fabiani, Ignacio; Rodríguez-Rodríguez, Álvaro; García-Gutiérrez, Mari-Cruz; Portale, Giuseppe; Castillejo, Marta; Ezquerra, Tiberio A

2015-04-07

The formation of laser-induced periodic surface structures (LIPSS) on model spin-coated polymer films has been followed in situ by grazing incidence small-angle X-ray scattering (GISAXS) using synchrotron radiation. The samples were irradiated at different repetition rates ranging from 1 up to 10 Hz by using the fourth harmonic of a Nd:YAG laser (266 nm) with pulses of 8 ns. Simultaneously, GISAXS patterns were acquired during laser irradiation. The variation of both the GISAXS signal with the number of pulses and the LIPSS period with laser irradiation time is revealing key kinetic aspects of the nanostructure formation process. By considering LIPSS as one-dimensional paracrystalline lattice and using a correlation found between the paracrystalline disorder parameter, g, and the number of reflections observed in the GISAXS patterns, the variation of the structural order of LIPSS can be assessed. The role of the laser repetition rate in the nanostructure formation has been clarified. For high pulse repetition rates (i.e., 10 Hz), LIPSS evolve in time to reach the expected period matching the wavelength of the irradiating laser. For lower pulse repetition rates LIPSS formation is less effective, and the period of the ripples never reaches the wavelength value. Results support and provide information on the existence of a feedback mechanism for LIPSS formation in polymer films.

Carbon nanotube thin film strain sensors: comparison between experimental tests and numerical simulations

NASA Astrophysics Data System (ADS)

Lee, Bo Mi; Loh, Kenneth J.

2017-04-01

Carbon nanotubes can be randomly deposited in polymer thin film matrices to form nanocomposite strain sensors. However, a computational framework that enables the direct design of these nanocomposite thin films is still lacking. The objective of this study is to derive an experimentally validated and two-dimensional numerical model of carbon nanotube-based thin film strain sensors. This study consisted of two parts. First, multi-walled carbon nanotube (MWCNT)-Pluronic strain sensors were fabricated using vacuum filtration, and their physical, electrical, and electromechanical properties were evaluated. Second, scanning electron microscope images of the films were used for identifying topological features of the percolated MWCNT network, where the information obtained was then utilized for developing the numerical model. Validation of the numerical model was achieved by ensuring that the area ratios (of MWCNTs relative to the polymer matrix) were equivalent for both the experimental and modeled cases. Strain sensing behavior of the percolation-based model was simulated and then compared to experimental test results.

Morphological control of conductive polymers utilized electrolysis polymerization technique: trial of fabricating biocircuit.

PubMed

Onoda, Mitsuyoshi

2014-10-01

Conductive polymers are a strong contender for making electronic circuits. The growth pattern in conductive polymer synthesis by the electrolysis polymerization method was examined. The growth pattern is deeply related to the coupling reaction of the radical cation and the deprotonation reaction following it and changes suddenly depending on the kind and concentration of the supporting electrolyte and the solvent used. That is, when the electrophilic substitution coupling reaction becomes predominant, the three-dimensional growth form is observed, and when the radical coupling reaction becomes predominant, the two-dimensional growth morphology is observed. In addition, the growth pattern can be comparatively easily controlled by changing the value of the polymerization constant current, and it is considered that the indicator and development for biocircuit research with neuron-type devices made of conjugated polymers was obtained.

Label free biosensor incorporating a replica-molded, vertically emitting distributed feedback laser

NASA Astrophysics Data System (ADS)

Lu, M.; Choi, S. S.; Wagner, C. J.; Eden, J. G.; Cunningham, B. T.

2008-06-01

A label free biosensor based upon a vertically emitting distributed feedback (DFB) laser has been demonstrated. The DFB laser comprises a replica-molded, one-dimensional dielectric grating coated with laser dye-doped polymer as the gain medium. Adsorption of biomolecules onto the laser surface alters the DFB laser emission wavelength, thereby permitting the kinetic adsorption of a protein polymer monolayer or the specific binding of small molecules to be quantified. A bulk sensitivity of 16.6nm per refractive index unit and the detection of a monolayer of the protein polymer poly(Lys, Phe) have been observed with this biosensor. The sensor represents a departure from conventional passive resonant optical sensors from the standpoint that the device actively generates its own narrowband high intensity output without stringent requirements on the coupling alignments, resulting in a simple, robust illumination and detection configuration.

Healable supramolecular polymers as organic metals.

PubMed

Armao, Joseph J; Maaloum, Mounir; Ellis, Thomas; Fuks, Gad; Rawiso, Michel; Moulin, Emilie; Giuseppone, Nicolas

2014-08-13

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice. Here we describe a one-dimensional supramolecular polymer in which photoinduced through-space charge-transfer complexes lead to highly coherent domains with delocalized electronic states displaying metallic behavior. We also reveal that diffusion of supramolecular polarons in the nanowires repairs structural defects thereby improving their conduction. The ability to access metallic properties from mendable self-assemblies extends the current understanding of both fields and opens a wide range of processing techniques for applications in organic electronics.

Increasing dimension of structures by 4D printing shape memory polymers via fused deposition modeling

NASA Astrophysics Data System (ADS)

Hu, G. F.; Damanpack, A. R.; Bodaghi, M.; Liao, W. H.

2017-12-01

The main objective of this paper is to introduce a 4D printing method to program shape memory polymers (SMPs) during fabrication process. Fused deposition modeling (FDM) as a filament-based printing method is employed to program SMPs during depositing the material. This method is implemented to fabricate complicated polymeric structures by self-bending features without need of any post-programming. Experiments are conducted to demonstrate feasibility of one-dimensional (1D)-to 2D and 2D-to-3D self-bending. It is shown that 3D printed plate structures can transform into masonry-inspired 3D curved shell structures by simply heating. Good reliability of SMP programming during printing process is also demonstrated. A 3D macroscopic constitutive model is established to simulate thermo-mechanical features of the printed SMPs. Governing equations are also derived to simulate programming mechanism during printing process and shape change of self-bending structures. In this respect, a finite element formulation is developed considering von-Kármán geometric nonlinearity and solved by implementing iterative Newton-Raphson scheme. The accuracy of the computational approach is checked with experimental results. It is demonstrated that the theoretical model is able to replicate the main characteristics observed in the experiments. This research is likely to advance the state of the art FDM 4D printing, and provide pertinent results and computational tool that are instrumental in design of smart materials and structures with self-bending features.

Water desorption from a confined biopolymer.

PubMed

Pradipkanti, L; Satapathy, Dillip K

2018-03-14

We study desorption of water from a confined biopolymer (chitosan thin films) by employing temperature dependent specular X-ray reflectivity and spectroscopic ellipsometry. The water desorption is found to occur via three distinct stages with significantly different desorption rates. The distinct rates of water desorption are attributed to the presence of different kinds of water with disparate mobilities inside the biopolymer film. We identify two characteristic temperatures (T c1 and T c2 ) at which the water desorption rate changes abruptly. Interestingly, the characteristic temperatures decrease with decreasing the film thickness. The thickness dependence of the characteristic temperature is interpreted in the context of a higher mobility of polymer chains at the free surface for polymers under one-dimensional confinement.

Stripe formation in an immiscible polymer blend under electric and shear-flow fields

NASA Astrophysics Data System (ADS)

Na, Yang-Ho; Shibuya, Tetsunori; Ujiie, Seiji; Nagaya, Tomoyuki; Orihara, Hiroshi

2008-04-01

We found a stripe formation in an emulsion of a liquid crystalline polymer (LCP) and a machine oil (OIL) in electric and shear fields. Through the simultaneous measurement with a confocal scanning laser microscope and a rheometer, it was clearly shown that the formation of stripes, which are periodically arrayed, leads to the increase of the shear stress. The droplets, which are one component of the emulsion, start to be connected at low electric fields and then change into the stripes with the increase of electric field. Finally, a three-dimensional network is formed at high electric fields. The period and fluctuation of the stripe structure were also investigated in detail.

One-dimensional transport equation models for sound energy propagation in long spaces: theory.

PubMed

Jing, Yun; Larsen, Edward W; Xiang, Ning

2010-04-01

In this paper, a three-dimensional transport equation model is developed to describe the sound energy propagation in a long space. Then this model is reduced to a one-dimensional model by approximating the solution using the method of weighted residuals. The one-dimensional transport equation model directly describes the sound energy propagation in the "long" dimension and deals with the sound energy in the "short" dimensions by prescribed functions. Also, the one-dimensional model consists of a coupled set of N transport equations. Only N=1 and N=2 are discussed in this paper. For larger N, although the accuracy could be improved, the calculation time is expected to significantly increase, which diminishes the advantage of the model in terms of its computational efficiency.

SU-E-T-243: MonteCarlo Simulation Study of Polymer and Radiochromic Gel for Three-Dimensional Proton Dose Distribution

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

Park, M; Jung, H; Kim, G

2014-06-01

Purpose: To estimate the three dimensional dose distributions in a polymer gel and a radiochromic gel by comparing with the virtual water phantom exposed to proton beams by applying Monte Carlo simulation. Methods: The polymer gel dosimeter is the compositeness material of gelatin, methacrylic acid, hydroquinone, tetrakis, and distilled water. The radiochromic gel is PRESAGE product. The densities of polymer and radiochromic gel were 1.040 and 1.0005 g/cm3, respectively. The shape of water phantom was a hexahedron with the size of 13 × 13 × 15 cm3. The proton beam energies of 72 and 116 MeV were used in themore » simulation. Proton beam was directed to the top of the phantom with Z-axis and the shape of beam was quadrangle with 10 × 10 cm2 dimension. The Percent depth dose and the dose distribution were evaluated for estimating the dose distribution of proton particle in two gel dosimeters, and compared with the virtual water phantom. Results: The Bragg-peak for proton particles in two gel dosimeters was similar to the virtual water phantom. Bragg-peak regions of polymer gel, radiochromic gel, and virtual water phantom were represented in the identical region (4.3 cm) for 72 MeV proton beam. For 116 MeV proton beam, the Bragg-peak regions of polymer gel, radiochromic gel, and virtual water phantom were represented in 9.9, 9.9 and 9.7 cm, respectively. The dose distribution of proton particles in polymer gel, radiochromic gel, and virtual water phantom was approximately identical in the case of 72 and 116 MeV energies. The errors for the simulation were under 10%. Conclusion: This work indicates the evaluation of three dimensional dose distributions by exposing proton particles to polymer and radiochromic gel dosimeter by comparing with the water phantom. The polymer gel and the radiochromic gel dosimeter show similar dose distributions for the proton beams.« less

Dynamics and rheology of finitely extensible polymer coils: An overview

NASA Astrophysics Data System (ADS)

Yao, Donggang

2017-05-01

One contemporary research issue in non-Newtonian fluid mechanics is to accurately and effectively model viscoelastic polymer flow of practical relevance. In the past several years, we have been working on the formulation of a finitely extensible coil model for polymer flow, particularly including these elements: (1) decoupled equations for kinematical and dynamical variables, (2) logarithmic relaxation at large deformation, (3) rotational retardation, (4) controllable straining, and (5) finite stretch. In this paper, we provide a constructive overview of this nonlinear coil formulation focusing on integration of these elements in a single, unified constitutive model with a minimal number of model parameters that are linked with corresponding physical processes. We also use this opportunity to share the rationale and thought process in the model development. In one particular implement of the general formulation, three parameters are used to tackle with the principal dynamics of a deforming polymer coil: one for finite stretch dictated by a ceiling stretch of the coil, the second one for rotational recovery/retardation, and the third one for adjusting stretch hardening of the rubbery coil. The new model, even in a single mode, is able to simultaneously predict practical material functions in simple shear and coaxial extension and to fit well to representative experimental data. Particularly in the steady-state (or quasi-steady state) flow case, a nearly closed-form stress to velocity gradient relationship can be derived with which shear thinning and elongational thickening can be simultaneously considered while computational advantages of a classical GNF model is retained. The model also fits reasonably well to representative experimental transient data for both shear and extension.

Two-dimensional interferometric characterization of laser-induced refractive index profiles in bulk Topas polymer

NASA Astrophysics Data System (ADS)

Hessler, Steffen; Rosenberger, Manuel; Schmauss, Bernhard; Hellmann, Ralf

2018-01-01

In this paper we precisely determine laser-induced refractive index profiles created in cyclic olefin copolymer Topas 6017 employing a sophisticated phase shifting Mach-Zehnder interferometry approach. Beyond the usual one-dimensional modification depth measurement we highlight that for straight waveguide structures also a two-dimensional refractive index distribution can be directly obtained providing full information of a waveguide's exact cross section and its gradient refractive index contrast. Deployed as direct data input in optical waveguide simulation, the evaluated 2D refractive index profiles permit a detailed calculation of the waveguides' actual mode profiles. Furthermore, conventional one-dimensional interferometric measurements for refractive index depth profiles with varying total imposed laser fluence of a 248 nm KrF excimer laser are included to investigate the effect on refractive index modification depth. Maximum surface refractive index increase turns out to attain up to 1.86 ·10-3 enabling laser-written optical waveguide channels. Additionally, a comprehensive optical material characterization in terms of dispersion, thermo-optic coefficient and absorption measurement of unmodified and UV-modified Topas 6017 is carried out.

Summary of mathematical models for a conventional and vertical junction photoconverter

NASA Technical Reports Server (NTRS)

Heinbockel, J. H.

1986-01-01

The geometry and computer programming for mathematical models of a one-dimensional conventional photoconverter, a one-dimensional vertical junction photoconverter, a three-dimensional conventinal photoconverter, and a three-dimensional vertical junction solar cell are discussed.

Hydrothermal synthesis and structural characterization of a novel three-dimensional supramolecular framework constructed by zinc salt and pyridine-2,5-dicarboxylate

NASA Astrophysics Data System (ADS)

Wang, Xinlong; Qin, Chao; Wang, Enbo; Hu, Changwen; Xu, Lin

2004-07-01

A novel metal-organic coordination polymer, [Zn(PDB)(H 2O) 2] 4 n (H 2PDB=pyridine-2,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Colorless crystals crystallized in the triclinic system, space group P-1, a=7.0562(14) Å, b=7.38526(15) Å, c=18.4611(4) Å, α=90.01(3)°, β=96.98(3)°, γ=115.67(3)°, V=859.1(3) Å 3, Z=1 and R=0.0334. The structure of the compound exhibits a novel three-dimensional supramolecular network, mainly based on multipoint hydrogen bonds originated from within and outside of a large 24-membered ring. Interestingly, the three-dimensional network consists of one-dimensional parallelogrammic channels in which coordinated water molecules point into the channel wall.

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

Xu, J.; Chen, T; Yang, C

Low-dimensional nanoparticles have a strong ability to induce the crystallization of polymer matrices. One-dimensional carbon nanotubes (CNTs) and two-dimensional graphene nanosheets (GNSs), both of which are both carbon-based nanoparticles, provide a good opportunity to investigate the effects of differently dimensional nanoparticles on the crystallization behavior of a polymer. For this purpose, respective nanocomposites of CNTs and GNSs with poly(L-lactide) (PLLA) as matrix were prepared by solution coagulation. Time-resolved Fourier-transform infrared spectroscopy (FTIR) and synchrotron wide-angle X-ray diffraction (WAXD) were performed to probe chain conformational changes and to determine the crystallization kinetics during the isothermal crystallization of the PLLA nanocomposites andmore » neat PLLA, especially in the early stages. Both CNTs and GNSs could serve as nucleating agents in accelerating the crystallization kinetics of PLLA; however, the ability of CNTs to induce crystallization was stronger than that of GNSs. On increasing the content of CNTs from 0.05 to 0.1 wt %, the induction period was shortened and the crystallization rate was enhanced, but the reverse situation was found for GNSs nanocomposites. In the case of neat PLLA, -CH{sub 3} interchain interactions preceded -(COC + CH{sub 3}) interchain interactions during the crystallization. Conversely, in the CNTs and GNSs nanocomposites, the conformational ordering began with -(COC + CH{sub 3}) interchain interactions, which resulted directly in a reduced induction period. Interchain interactions of this type could be explained in terms of surface-induced conformational order (SICO). Finally, the effect of the dimensionality of the nanoparticles on the crystallization behavior of PLLA is discussed.« less

Effects of extensional rates on characteristic scales of two-dimensional turbulence in polymer solutions

NASA Astrophysics Data System (ADS)

Hidema, R.

2014-08-01

In order to study the effects of extensional viscosities on turbulent drag reduction, experimental studies using two-dimensional turbulence have been made. Anisotropic structures and variations of energy transfer induced by polymers are considered. Polyethyleneoxide and hydroxypropyl cellulose having different flexibility, which is due to different characteristics of extensional viscosity, are added to 2D turbulence. Variations of the turbulence were visualized by interference patterns of 2D flow, and were analysed by an image processing. The effects of polymers on turbulence in the streamwise and normal directions were also analysed by 2D Fourier transform. In addition, characteristic scales in 2D turbulence were analysed by wavelet transform.

Three-Dimensional Large Screen Display Using Polymer-Dispersed Liquid-Crystal Light Valves and a Schlieren Optical System: Proposal and Basic Experiments

NASA Astrophysics Data System (ADS)

Takizawa, Kuniharu

A novel three-dimensional (3-D) projection display used with polarized eyeglasses is proposed. It consists of polymer-dispersed liquid crystal-light valves that modulate the illuminated light based on light scattering, a polarization beam splitter, and a Schlieren projection system. The features of the proposed display include a 3-D image display with a single projector, half size and half power consumption compared with a conventional 3-D projector with polarized glasses. Measured electro-optic characteristics of a polymer-dispersed liquid-crystal cell inserted between crossed polarizers suggests that the proposed display achieves small cross talk and high-extinction ratio.

Monosaccharides as Versatile Units for Water-Soluble Supramolecular Polymers.

PubMed

Leenders, Christianus M A; Jansen, Gijs; Frissen, Martijn M M; Lafleur, René P M; Voets, Ilja K; Palmans, Anja R A; Meijer, E W

2016-03-18

We introduce monosaccharides as versatile water-soluble units to compatibilise supramolecular polymers based on the benzene-1,3,5-tricarboxamide (BTA) moiety with water. A library of monosaccharide-based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α-glucose, β-glucose, α-mannose and α-galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one-dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self-assembly process is operative and that the introduction of different monosaccharides does not significantly change the self- assembly behaviour. Finally, we investigate the potential of post-assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal coordination polymer derived mesoporous Co3O4 nanorods with uniform TiO2 coating as advanced anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Geng, Hongbo; Ang, Huixiang; Ding, Xianguang; Tan, Huiteng; Guo, Guile; Qu, Genlong; Yang, Yonggang; Zheng, Junwei; Yan, Qingyu; Gu, Hongwei

2016-01-01

In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling.In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08570e

One-dimensional nanomaterials for energy storage

NASA Astrophysics Data System (ADS)

Chen, Cheng; Fan, Yuqi; Gu, Jianhang; Wu, Liming; Passerini, Stefano; Mai, Liqiang

2018-03-01

The search for higher energy density, safer, and longer cycling-life energy storage systems is progressing quickly. One-dimensional (1D) nanomaterials have a large length-to-diameter ratio, resulting in their unique electrical, mechanical, magnetic and chemical properties, and have wide applications as electrode materials in different systems. This article reviews the latest hot topics in applying 1D nanomaterials, covering both their synthesis and their applications. 1D nanomaterials can be grouped into the categories: carbon, silicon, metal oxides, and conducting polymers, and we structure our discussion accordingly. Then, we survey the unique properties and application of 1D nanomaterials in batteries and supercapacitors, and provide comments on the progress and advantages of those systems, paving the way for a better understanding of employing 1D nanomaterials for energy storage.

Functional Polymers and Nanocomposites for 3D Printing of Smart Structures and Devices.

PubMed

Nadgorny, Milena; Ameli, Amir

2018-05-30

Three-dimensional printing (3DP) has attracted a considerable amount of attention during the past years, being globally recognized as one of the most promising and revolutionary manufacturing technologies. Although the field is rapidly evolving with significant technological advancements, materials research remains a spotlight of interest, essential for the future developments of 3DP. Smart polymers and nanocomposites, which respond to external stimuli by changing their properties and structure, represent an important group of materials that hold a great promise for the fabrication of sensors, actuators, robots, electronics, and medical devices. The interest in exploring functional materials and their 3DP is constantly growing in an attempt to meet the ever-increasing manufacturing demand of complex functional platforms in an efficient manner. In this review, we aim to outline the recent advances in the science and engineering of functional polymers and nanocomposites for 3DP technologies. The report covers temperature-responsive polymers, polymers and nanocomposites with electromagnetic, piezoresistive and piezoelectric behaviors, self-healing polymers, light- and pH-responsive materials, and mechanochromic polymers. The main objective is to link the performance and functionalities to the fundamental properties, chemistry, and physics of the materials, and to the process-driven characteristics, in an attempt to provide a multidisciplinary image and a deeper understanding of the topic. The challenges and opportunities for future research are also discussed.

Novel Polyurethane Matrix Systems Reveal a Particular Sustained Release Behavior Studied by Imaging and Computational Modeling.

PubMed

Campiñez, María Dolores; Caraballo, Isidoro; Puchkov, Maxim; Kuentz, Martin

2017-07-01

The aim of the present work was to better understand the drug-release mechanism from sustained release matrices prepared with two new polyurethanes, using a novel in silico formulation tool based on 3-dimensional cellular automata. For this purpose, two polymers and theophylline as model drug were used to prepare binary matrix tablets. Each formulation was simulated in silico, and its release behavior was compared to the experimental drug release profiles. Furthermore, the polymer distributions in the tablets were imaged by scanning electron microscopy (SEM) and the changes produced by the tortuosity were quantified and verified using experimental data. The obtained results showed that the polymers exhibited a surprisingly high ability for controlling drug release at low excipient concentrations (only 10% w/w of excipient controlled the release of drug during almost 8 h). The mesoscopic in silico model helped to reveal how the novel biopolymers were controlling drug release. The mechanism was found to be a special geometrical arrangement of the excipient particles, creating an almost continuous barrier surrounding the drug in a very effective way, comparable to lipid or waxy excipients but with the advantages of a much higher compactability, stability, and absence of excipient polymorphism.

Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications.

PubMed

Miao, Shida; Zhu, Wei; Castro, Nathan J; Leng, Jinsong; Zhang, Lijie Grace

2016-10-01

The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term "4D printing" refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from -8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at -18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of novel and functional biomedical scaffolds with advanced 4D printing technology and highly biocompatible smart biomaterials.

Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications

PubMed Central

Miao, Shida; Zhu, Wei; Castro, Nathan J.; Leng, Jinsong

2016-01-01

The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term “4D printing” refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from −8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at −18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of novel and functional biomedical scaffolds with advanced 4D printing technology and highly biocompatible smart biomaterials. PMID:28195832

Modeling liquid crystal polymeric devices

NASA Astrophysics Data System (ADS)

Gimenez Pinto, Vianney Karina

The main focus of this work is the theoretical and numerical study of materials that combine liquid crystal and polymer. Liquid crystal elastomers are polymeric materials that exhibit both the ordered properties of the liquid crystals and the elastic properties of rubbers. Changing the order of the liquid crystal molecules within the polymer network can induce shape change. These materials are very valuable for applications such as actuators, sensors, artificial muscles, haptic displays, etc. In this work we apply finite element elastodynamics simulations to study the temperature induced shape deformation in nematic elastomers with complex director microstructure. In another topic, we propose a novel numerical method to model the director dynamics and microstructural evolution of three dimensional nematic and cholesteric liquid crystals. Numerical studies presented in this work are in agreement with experimental observations and provide insight into the design of application devices.

Syntheses, structures and characterization of isomorphous CoII and NiII coordination polymers based on 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole and benzene-1,4-dicarboxylate.

PubMed

Huang, Qiu Ying; Zhao, Yang; Meng, Xiang Ru

2017-08-01

Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal-organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen-bond acceptors and donors in the assembly of supramolecular structures. Nitrogen-heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN 3 }cobalt(II)]-μ 2 -benzene-1,4-dicarboxylato-κ 2 O 1 :O 4 ] dihydrate], {[Co(C 8 H 4 O 4 )(C 12 H 11 N 4 ) 2 (H 2 O) 2 ]·2H 2 O} n , (I), and catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN 3 }nickel(II)]-μ 2 -benzene-1,4-dicarboxylato-κ 2 O 1 :O 4 ] dihydrate], {[Ni(C 8 H 4 O 4 )(C 12 H 11 N 4 ) 2 (H 2 O) 2 ]·2H 2 O} n , (II), the Co II or Ni II ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole ligands coordinate to the Co II or Ni II centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one-dimensional chains are further connected through O-H...O, O-H...N and N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.

A Kirigami shape memory polymer honeycomb concept for deployment

NASA Astrophysics Data System (ADS)

Neville, Robin M.; Chen, Jianguo; Guo, Xiaogang; Zhang, Fenghua; Wang, Wenxin; Dobah, Yousef; Scarpa, Fabrizio; Leng, Jinsong; Peng, Hua-Xin

2017-05-01

We present a shape memory polymer (SMP) honeycomb with tuneable and shape morphing mechanical characteristics. Kirigami (Origami with cutting allowed) techniques have been used to design and manufacture the honeycomb. The cellular structure described in this work has styrene SMP hinges that create the shape change and the deployment actuation. To create a large volumetric deployment, the Kirigami open honeycomb configuration has been designed by setting an initial three-dimensional re-entrant auxetic (negative Poisson’s ratio) configuration, while the final honeycomb shape assume a convex (positive Poisson’s ratio) layout. A model was developed to predict the shape change of the structure, and compared to experimental results from a demonstrator honeycomb deployment test.

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

Luo, Qianqian; Han, Ying; Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn

One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel andmore » linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.« less

Role of cell deformability in the two-dimensional melting of biological tissues

NASA Astrophysics Data System (ADS)

Li, Yan-Wei; Ciamarra, Massimo Pica

2018-04-01

The size and shape of a large variety of polymeric particles, including biological cells, star polymers, dendrimes, and microgels, depend on the applied stresses as the particles are extremely soft. In high-density suspensions these particles deform as stressed by their neighbors, which implies that the interparticle interaction becomes of many-body type. Investigating a two-dimensional model of cell tissue, where the single particle shear modulus is related to the cell adhesion strength, here we show that the particle deformability affects the melting scenario. On increasing the temperature, stiff particles undergo a first-order solid/liquid transition, while soft ones undergo a continuous solid/hexatic transition followed by a discontinuous hexatic/liquid transition. At zero temperature the melting transition driven by the decrease of the adhesion strength occurs through two continuous transitions as in the Kosterlitz, Thouless, Halperin, Nelson, and Young scenario. Thus, there is a range of adhesion strength values where the hexatic phase is stable at zero temperature, which suggests that the intermediate phase of the epithelial-to-mesenchymal transition could be hexatic type.

Modeling pressure-driven assembly of polymer coated nanoparticles

NASA Astrophysics Data System (ADS)

Lane, J. Matthew D.; Salerno, K. Michael; Grest, Gary S.; Fan, Hongyou

2017-06-01

High-pressure experiments have successfully produced a variety of gold nanostructures by compressing polymer coated spherical nanoparticles. We apply atomistic simulation to understand the role of the soft polymer response in determining the pressure-driven assembly of gold nanostructures. Quasi-isentropic experiments have shown that 1D, 2D and 3D nanostructures can be formed and recovered from dynamic compression of fcc superlattices of alkanethiol-coated gold nanocrystals on Sandia's Veloce pulsed power accelerator. Molecular modeling has shown that the dimensionality of the final structures depends on the orientation of the superlattice and the uniaxial loading. We describe the role of coating ligand length and grafting density, on ligand migration and deformation processes during pressure-driven coalescence of the cores into permanent nanowires, nanosheets and 3D structures. The role of uniaxial vs isotropic pressure and the effects of compression along various superlattice orientations will be discussed. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Electro-osmotic flow in coated nanocapillaries: a theoretical investigation.

PubMed

Marini Bettolo Marconi, Umberto; Monteferrante, Michele; Melchionna, Simone

2014-12-14

Motivated by recent experiments, we present a theoretical investigation of how the electro-osmotic flow occurring in a capillary is modified when its charged surfaces are coated with charged polymers. The theoretical treatment is based on a three-dimensional model consisting of a ternary fluid-mixture, representing the solvent and two species for the ions, confined between two parallel charged plates decorated with a fixed array of scatterers representing the polymer coating. The electro-osmotic flow, generated by a constant electric field applied in a direction parallel to the plates, is studied numerically by means of Lattice Boltzmann simulations. In order to gain further understanding we performed a simple theoretical analysis by extending the Stokes-Smoluchowski equation to take into account the porosity induced by the polymers in the region adjacent to the walls. We discuss the nature of the velocity profiles by focusing on the competing effects of the polymer charges and the frictional forces they exert. We show evidence of the flow reduction and of the flow inversion phenomenon when the polymer charge is opposite to the surface charge. By using the density of polymers and the surface charge as control variables, we propose a phase diagram that discriminates the direct and the reversed flow regimes and determines their dependence on the ionic concentration.

Properties of Multiphase Polyurethane Systems.

DTIC Science & Technology

1983-07-01

segment - diphenylmethane-diisocyanate/ N - methyldiethanolamine (MDI/ MDEA ). Each polymer was synthesized using a two step reaction technique. The number...OF MULTIPHASE POLYURETHANE SYSTEMS Final Report for Period July 1, 1982-June 30, 1983 Naval Air Systems Command Code 5304 C2 ONavy Contract # N 00019...and COB, UA groups. The existence of 3-dimensional hydrogen bonding (two C-O groups bonded to one N -H group) should shift the COB,UA peak to lower

Optical sensor in planar configuration based on multimode interference

NASA Astrophysics Data System (ADS)

Blahut, Marek

2017-08-01

In the paper a numerical analysis of optical sensors based on multimode interference in planar one-dimensional step-index configuration is presented. The structure consists in single-mode input and output waveguides and multimode waveguide which guide only few modes. Material parameters discussed refer to a SU8 polymer waveguide on SiO2 substrate. The optical system described will be designed to the analysis of biological substances.

From supramolecular polymers to multi-component biomaterials.

PubMed

Goor, Olga J G M; Hendrikse, Simone I S; Dankers, Patricia Y W; Meijer, E W

2017-10-30

The most striking and general property of the biological fibrous architectures in the extracellular matrix (ECM) is the strong and directional interaction between biologically active protein subunits. These fibers display rich dynamic behavior without losing their architectural integrity. The complexity of the ECM taking care of many essential properties has inspired synthetic chemists to mimic these properties in artificial one-dimensional fibrous structures with the aim to arrive at multi-component biomaterials. Due to the dynamic character required for interaction with natural tissue, supramolecular biomaterials are promising candidates for regenerative medicine. Depending on the application area, and thereby the design criteria of these multi-component fibrous biomaterials, they are used as elastomeric materials or hydrogel systems. Elastomeric materials are designed to have load bearing properties whereas hydrogels are proposed to support in vitro cell culture. Although the chemical structures and systems designed and studied today are rather simple compared to the complexity of the ECM, the first examples of these functional supramolecular biomaterials reaching the clinic have been reported. The basic concept of many of these supramolecular biomaterials is based on their ability to adapt to cell behavior as a result of dynamic non-covalent interactions. In this review, we show the translation of one-dimensional supramolecular polymers into multi-component functional biomaterials for regenerative medicine applications.

Reversibility and intermediate steps as key tools for the growth of extended ordered polymers via on-surface synthesis

NASA Astrophysics Data System (ADS)

Di Giovannantonio, Marco; Contini, Giorgio

2018-03-01

Surface-confined polymerization is a bottom-up strategy to create one- and two-dimensional covalent organic nanostructures with a π-conjugated backbone, which are suitable to be employed in real-life electronic devices, due to their high mechanical resistance and electronic charge transport efficiency. This strategy makes it possible to change the properties of the final nanostructures by a careful choice of the monomer architecture (i.e. of its constituent atoms and their spatial arrangement). Several chemical reactions have been proven to form low-dimensional polymers on surfaces, exploiting a variety of precursors in combination with metal (e.g. Cu, Ag, Au) and insulating (e.g. NaCl, CaCO3) surfaces. One of the main challenges of such an approach is to obtain nanostructures with long-range order, to boost the conductance performances of these materials. Most of the exploited chemical reactions use irreversible coupling between the monomers and, as a consequence, the resulting structures often suffer from poor order and high defect density. This review focuses on the state-of-the-art surface-confined polymerization reactions, with particular attention paid to reversible coupling pathways and irreversible processes including intermediate states, which are key aspects to control to increase the order of the final nanostructure.

Computational Modeling of Hydroxypropyl-Methylcellulose Acetate Succinate (HPMCAS) and Phenytoin Interactions: A Systematic Coarse-Graining Approach.

PubMed

Huang, Wenjun; Mandal, Taraknath; Larson, Ronald G

2017-03-06

We present coarse-grained (CG) force fields for hydroxypropyl-methylcellulose acetate succinate (HPMCAS) polymers and the drug molecule phenytoin using a bead/stiff spring model, with each bead representing a HPMCAS monomer or monomer side group (hydroxypropyl acetyl, acetyl, or succinyl) or a single phenytoin ring. We obtain the bonded and nonbonded interaction parameters in our CG model using the RDFs from atomistic simulations of short HPMCAS model oligomers (20-mer) and atomistic simulations of phenytoin molecules. The nonbonded interactions are modeled using a LJ 12-6 potential, with separate parameters for each monomer substitution type, which allows heterogeneous polymer chains to be modeled. The cross interaction terms between the polymer and phenytoin CG beads are obtained explicitly from atomistic level polymer-phenytoin simulations, rather than from mixing rules. We study the solvation behavior of 50-mer and 100-mer polymer chains and find chain-length-dependent aggregation. We also compare the phenytoin CG force field developed in this work with that in Mandal et al. (Soft Matter, 2016, 12, 8246-8255) and conclude both are suitable for studying the interaction between polymer and drug in solvated solid dispersion formulation, in the absence of drug crystallization. Finally, we present simulations of heterogeneous HPMCAS model polymer chains and phenytoin molecules. Polymer and drug form a complex in a short period of simulation time due to strong intermolecular interactions. Moreover, the protonated polymer chains are more effective than deprotonated ones in inhibiting the drug aggregation in the polymer-drug complex.

Heat transfer and thermal management studies of lithium polymer batteries for electric vehicle applications

NASA Astrophysics Data System (ADS)

Song, Li

The thermal conductivities of the polymer electrolyte and composite cathode are important parameters characterizing heat transport in lithium polymer batteries. The thermal conductivities of lithium polymer electrolytes, including poly-ethylene oxide (PEO), PEO-LiClO4, PEO-LiCF3SO 3, PEO-LiN(CF3SO2)2, PEO-LiC(CF 3SO2)3, and the thermal conductivities of TiS 2 and V6O13 composite cathodes, were measured over the temperature range from 25°C to 150°C by a guarded heat flow meter. The thermal conductivities of the electrolytes were found to be relatively constant for the temperature and for electrolytes with various concentrations of the lithium salt. The thermal conductivities of the composite cathodes were found to increase with the temperature below the melting temperature of the polymer electrolyte and only slightly increase above the melting temperature. Three different lithium polymer cells, including Li/PEO-LiCF3 S O3/TiS2, Li/PEO-LiC(CF3 S O2)3/V6 O13, and Li/PEO-LiN(CF3 S O2)2/ Li1+x Mn2 O4 were prepared and their discharge curves, along with heat generation rates, were measured at various galvanostatic discharge current densities, and at different temperature (70°C, 80°C and 90°C), by a potentiostat/galvanostat and an isothermal microcalorimeter. The thermal stability of a lithium polymer battery was examined by a linear perturbation analysis. In contrast to the thermal conductivity, the ionic conductivity of polymer electrolytes for lithium-polymer cell increases greatly with increasing temperature, an instability could arise from this temperature dependence. The numerical calculations, using a two dimensional thermal model, were carried out for constant potential drop across the electrolyte, for constant mean current density and for constant mean cell output power. The numerical calculations were approximately in agreement with the linear perturbation analysis. A coupled mathematical model, including electrochemical and thermal components, was developed to study the heat transfer and thermal management of lithium polymer batteries. The results calculated from the model, including temperature distributions, and temperatures at different stages of discharge are significantly different from those calculated from the thermal model. The discharge curves and heat generation rates calculated by the electrochemical-thermal model were in agreement with the experimental results. Different thermal management approaches, including a variable conductance insulation enclosure were studied.

Applicability of electrospun polypropylene carbonate polymers as a drug carrier for sirolimus.

PubMed

Sun, Hourong; Gu, Xinghua; Liu, Kai; Fang, Changcun; Tang, Mengmeng

2017-06-01

Polypropylene carbonate (PPC), a biodegradable aliphatic polyester, exhibits one particular advantage over other polyesters, which is that following degradation in vivo, it primarily produces H2O and CO2, causing minimal side effects. Although PPC exhibits limited mechanical strength, and is therefore not able to serve as a scaffold to support tissue regeneration, it may be suitable for drug delivery; however, this requires further investigation. In the present study, electrospinning was applied to generate PPC polymers containing sirolimus, a cell growth‑inhibiting drug which is used to treat restenosis. The properties of PPC‑sirolimus polymers were examined using scanning electron microscopy, differential scanning calorimetry and in vitro degradation assays. Drug loading and entrapment efficiency were determined, and in vitro sirolimus‑release from the polymer was assessed. Furthermore, the effect of PPC‑sirolimus polymers on cell growth was measured using an MTT assay in vitro. The results of the present study demonstrated that electrospun PPC polymers formed a uniform three‑dimensional, grid‑intertwined, net‑like structure; the surface of the polymers was smooth and the diameter was ~3 µm. Differential scanning calorimetry analysis demonstrated that sirolimus existed in an amorphous state in the polymer. Following soaking in PBS for 4 weeks, the polymer swelled and the net‑like structure broke down and fragmented. Sirolimus loading and entrapment efficiency were 10.3±3.2 and 95.1±10.6%, respectively. Sirolimus‑release from PPC‑sirolimus polymers continued for 28 days in PBS. PPC‑sirolimus markedly inhibited the growth of rat aortic adventitial fibroblast cells, an effect which was not observed with PPC alone. The results of the present study suggest that PPC polymers are a promising alternative drug carrier for sirolimus.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

PubMed

Chawla, Parul; Singh, Son; Sharma, Shailesh Narain

2014-01-01

In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern-Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor-acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

On compression and damage evolution in two thermoplastics

DOE PAGES

Bourne, N. K.; Garcea, S. C.; Eastwood, D. S.; ...

2017-01-18

The well-known Taylor cylinder impact test, which follows the impact of a flat-ended cylindrical rod onto a rigid stationary anvil, is conducted over a range of impact speeds for two polymers, polytetrafluoroethylene (PTFE) and polyetheretherketone (PEEK). In previous work, experiments and a model were developed to capture the deformation behaviour of the cylinder after impact. These works showed a region in which spatial and temporal variation of both longitudinal and radial deformation provided evidence of changes in phase within the material. In this further series of experiments, this region is imaged in a range of impacted targets at the Diamondmore » synchrotron. Further techniques were fielded to resolve compressed regions within the recovered polymer cylinders that showed a fracture zone in the impact region. The combination of macroscopic high-speed photography and three-dimensional X-ray imaging has identified the development of failure with these polymers and shown that there is no abrupt transition in behaviours but rather a continuous range of responses to competing operating mechanisms. The behaviours noted in PEEK in these polymers show critical gaps in understanding of polymer high strain-rate response.« less

Role of Elasto-Inertial Turbulence in Polymer Drag Reduction

NASA Astrophysics Data System (ADS)

Dubief, Yves; Sid, Samir; Terrapon, Vincent

2017-11-01

Elasto-Inertial Turbulence (EIT) is a peculiar state of turbulence found in dilute polymer solutions flowing in parallel wall flows over a wide range of Reynolds numbers. At subcritical Reynolds numbers, appropriate boundary conditions trigger EIT, a self-sustaining cycle of energy transfers between thin sheets of stretched polymers and velocity perturbations, which translates into an increase of friction drag. For critical and supercritical Reynolds numbers, polymer additives may lead to significant drag reduction, bounded by the asymptotic state known as Maximum Drag Reduction (MDR). The present research investigates the role of EIT in the dynamics of critical and supercritical Reynolds number wall flows. Using high-fidelity direct numerical simulations of channel flows and the FENE-P model, we establish that (i) EIT is two-dimensional, (ii) the scales essential to the existence of EIT are sub-Kolmogorov, and (iii) EIT drives MDR at low and possibly moderate Reynolds number turbulent flows. These findings were validated in two different codes and using unprecedented resolutions for polymer flows. YD is grateful for the support of Binational Science Foundation. SS and VT acknowledges Fonds de la Recherche Scientifique (FNRS), MarieCurie Career Integration Grant and computing allocation from University of Liege and PRACE.

Conducting polymer nanowire arrays for high performance supercapacitors.

PubMed

Wang, Kai; Wu, Haiping; Meng, Yuena; Wei, Zhixiang

2014-01-15

This Review provides a brief summary of the most recent research developments in the fabrication and application of one-dimensional ordered conducting polymers nanostructure (especially nanowire arrays) and their composites as electrodes for supercapacitors. By controlling the nucleation and growth process of polymerization, aligned conducting polymer nanowire arrays and their composites with nano-carbon materials can be prepared by employing in situ chemical polymerization or electrochemical polymerization without a template. This kind of nanostructure (such as polypyrrole and polyaniline nanowire arrays) possesses high capacitance, superior rate capability ascribed to large electrochemical surface, and an optimal ion diffusion path in the ordered nanowire structure, which is proved to be an ideal electrode material for high performance supercapacitors. Furthermore, flexible, micro-scale, threadlike, and multifunctional supercapacitors are introduced based on conducting polyaniline nanowire arrays and their composites. These prototypes of supercapacitors utilize the high flexibility, good processability, and large capacitance of conducting polymers, which efficiently extend the usage of supercapacitors in various situations, and even for a complicated integration system of different electronic devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template directed assembly of nanoelements in viscous polymer environments

NASA Astrophysics Data System (ADS)

Modi, Satyamkumar

Polymer melt-based manufacturing methods, such as injection molding, offer the potential of directly fabricating three-dimensional parts with nanostructured surfaces in a one-step, high-rate, and solventless process. Electrophoretic deposition has the potential to produce in-mold assembly of nanoparticles during injection molding. The process is fast, is cost effective and can be automated. This electrophoretic deposition, however, has been performed from low-viscosity media and polymer melts are far more viscous. This research provided a fundamental understanding of the electrophoretic deposition process in viscous media. Electrophoresis was performed using a model system of carbon black and polystyrene in tetrahydrofuran (THF). Examined were the effects of processing parameters, polystyrene molecular weight, and carbon black charge. The presence of polystyrene did not prevent deposition of carbon black, but deposition rates decreased at shorter deposition times; deposition was not linear with increasing applied voltage; and greater solution concentrations reduced the critical voltages. A comparison of experimental data with Hamaker's model showed that about 1.6% of the available polystyrene was initially deposited with the carbon black. At voltages above the critical voltage, the deposited mass indicated formation of electrically insulating layers on the electrodes. Increases in polystyrene molecular weight reduced the electrophoretic deposition of the carbon black particles due to increases in suspension viscosity and preferential adsorption of the longer polystyrene chains on the carbon black particles. At low deposition times (≤ 5 seconds), only carbon black deposited onto the electrodes. For longer deposition times, polystyrene co-deposited with the carbon black, with the amount of polystyrene increasing with molecular weight and decreasing with greater charge on the polystyrene molecules. The additional of function groups to the carbon black surface decoupled the carbon black and polystyrene, however, the deposition of the carbon black particles, followed by deposition of a thick layer of polystyrene was observed. This polystyrene deposition was present regardless of the applied voltage, the deposition time, the polystyrene molecular weight, polystyrene material (i.e., charge), and solvent polarity. This deposition behavior suggests that use of lower molecular polymers and unmodified carbon blacks, and control of electrical properties will permit electrophoretic deposition of nanoparticles from polymer melts.

A spatially nonlocal model for polymer-penetrant diffusion

NASA Astrophysics Data System (ADS)

Edwards, D. A.

Diffusion of a penetrant in a polymer entanglement network cannot be described by Fick's Law alone; rather, one must incorporate other nonlocal effects. In contrast to previous viscoelastic models which have modeled these effects through hereditary integrals in time, a new model is presented exploiting the disparate lengths of the polymer in the glassy (dry) and rubbery (saturated) states. This model leads to a partial integrodifferential equation which is nonlocal in space. The system is recast as a moving boundary-value problem between sets of coupled partial differential equations. Using singular perturbation techniques, sorption in a semi-infinite polymer is studied on several time scales with varying exposed interface conditions. Though some of the results match with those from viscoelastic models, new physically relevant behaviors also appear. These include the formation of stopping fronts and overshoot in the pseudostress.

Optimizing separations in online comprehensive two‐dimensional liquid chromatography

PubMed Central

Gargano, Andrea F.G.; Schoenmakers, Peter J.

2017-01-01

Abstract Online comprehensive two‐dimensional liquid chromatography has become an attractive option for the analysis of complex nonvolatile samples found in various fields (e.g. environmental studies, food, life, and polymer sciences). Two‐dimensional liquid chromatography complements the highly popular hyphenated systems that combine liquid chromatography with mass spectrometry. Two‐dimensional liquid chromatography is also applied to the analysis of samples that are not compatible with mass spectrometry (e.g. high‐molecular‐weight polymers), providing important information on the distribution of the sample components along chemical dimensions (molecular weight, charge, lipophilicity, stereochemistry, etc.). Also, in comparison with conventional one‐dimensional liquid chromatography, two‐dimensional liquid chromatography provides a greater separation power (peak capacity). Because of the additional selectivity and higher peak capacity, the combination of two‐dimensional liquid chromatography with mass spectrometry allows for simpler mixtures of compounds to be introduced in the ion source at any given time, improving quantitative analysis by reducing matrix effects. In this review, we summarize the rationale and principles of two‐dimensional liquid chromatography experiments, describe advantages and disadvantages of combining different selectivities and discuss strategies to improve the quality of two‐dimensional liquid chromatography separations. PMID:29027363

Laser range profile of cones

NASA Astrophysics Data System (ADS)

Zhou, Wenzhen; Gong, Yanjun; Wang, Mingjun; Gong, Lei

2016-10-01

technology. Laser one-dimensional range profile can reflect the characteristics of the target shape and surface material. These techniques were motivated by applications of laser radar to target discrimination in ballistic missile defense. The radar equation of pulse laser about cone is given in this paper. This paper demonstrates the analytical model of laser one-dimensional range profile of cone based on the radar equation of the pulse laser. Simulations results of laser one-dimensional range profiles of some cones are given. Laser one-dimensional range profiles of cone, whose surface material with diffuse lambertian reflectance, is given in this paper. Laser one-dimensional range profiles of cone, whose surface mater with diffuse materials whose retroreflectance can be modeled closely with an exponential term that decays with increasing incidence angles, is given in this paper. Laser one-dimensional range profiles of different pulse width of cone is given in this paper. The influences of surface material, pulse width, attitude on the one-dimensional range are analyzed. The laser two-dimensional range profile is two-dimensional scattering imaging of pulse laser of target. The two-dimensional range profile of roughness target can provide range resolved information. An analytical model of two-dimensional laser range profile of cone is proposed. The simulations of two-dimensional laser range profiles of some cones are given. Laser two-dimensional range profiles of cone, whose surface mater with diffuse lambertian reflectance, is given in this paper. Laser two-dimensional range profiles of cone, whose surface mater with diffuse materials whose retroreflectance can be modeled closely with an exponential term that decays with increasing incidence angles, is given in this paper. The influence of pulse width, surface material on laser two-dimensional range profile is analyzed. Laser one-dimensional range profile and laser two-dimensional range profile are called as laser range profile (LRP).

Role of non-equilibrium conformations on driven polymer translocation.

PubMed

Katkar, H H; Muthukumar, M

2018-01-14

One of the major theoretical methods in understanding polymer translocation through a nanopore is the Fokker-Planck formalism based on the assumption of quasi-equilibrium of polymer conformations. The criterion for applicability of the quasi-equilibrium approximation for polymer translocation is that the average translocation time per Kuhn segment, ⟨τ⟩/N K , is longer than the relaxation time τ 0 of the polymer. Toward an understanding of conditions that would satisfy this criterion, we have performed coarse-grained three dimensional Langevin dynamics and multi-particle collision dynamics simulations. We have studied the role of initial conformations of a polyelectrolyte chain (which were artificially generated with a flow field) on the kinetics of its translocation across a nanopore under the action of an externally applied transmembrane voltage V (in the absence of the initial flow field). Stretched (out-of-equilibrium) polyelectrolyte chain conformations are deliberately and systematically generated and used as initial conformations in translocation simulations. Independent simulations are performed to study the relaxation behavior of these stretched chains, and a comparison is made between the relaxation time scale and the mean translocation time (⟨τ⟩). For such artificially stretched initial states, ⟨τ⟩/N K < τ 0 , demonstrating the inapplicability of the quasi-equilibrium approximation. Nevertheless, we observe a scaling of ⟨τ⟩ ∼ 1/V over the entire range of chain stretching studied, in agreement with the predictions of the Fokker-Planck model. On the other hand, for realistic situations where the initial artificially imposed flow field is absent, a comparison of experimental data reported in the literature with the theory of polyelectrolyte dynamics reveals that the Zimm relaxation time (τ Zimm ) is shorter than the mean translocation time for several polymers including single stranded DNA (ssDNA), double stranded DNA (dsDNA), and synthetic polymers. Even when these data are rescaled assuming a constant effective velocity of translocation, it is found that for flexible (ssDNA and synthetic) polymers with N K Kuhn segments, the condition ⟨τ⟩/N K < τ Zimm is satisfied. We predict that for flexible polymers such as ssDNA, a crossover from quasi-equilibrium to non-equilibrium behavior would occur at N K ∼ O(1000).

Small-Angle Neutron Scattering Study of Interplay of Attractive and Repulsive Interactions in Nanoparticle-Polymer System.

PubMed

Kumar, Sugam; Aswal, Vinod K; Kohlbrecher, Joachim

2016-02-16

The phase behavior of nanoparticle (silica)-polymer (polyethylene glycol) system without and with an electrolyte (NaCl) has been studied. It is observed that nanoparticle-polymer system behaves very differently in the presence of electrolyte. In the absence of electrolyte, the nanoparticle-polymer system remains in one-phase even at very high polymer concentrations. On the other hand, a re-entrant phase behavior is found in the presence of electrolyte, where one-phase (individual) system undergoes two-phase (nanoparticle aggregation) and then back to one-phase with increasing polymer concentration. The regime of two-phase system has been tuned by varying the electrolyte concentration. The polymer concentration range over which the two-phase system exists is significantly enhanced with the increase in the electrolyte concentration. These systems have been characterized by small-angle neutron scattering (SANS) experiments of contrast-marching the polymer to the solvent. The data are modeled using a two-Yukawa potential accounting for both attractive and repulsive parts of the interaction between nanoparticles. The phase behavior of nanoparticle-polymer system is explained by interplay of attractive (polymer-induced attractive depletion between nanoparticles) and repulsive (nanoparticle-nanoparticle electrostatic repulsion and polymer-polymer repulsion) interactions present in the system. In the absence of electrolyte, the strong electrostatic repulsion between nanoparticles dominates over the polymer-induced depletion attraction and the nanoparticle system remains in one-phase. With addition of electrolyte, depletion attraction overcomes electrostatic repulsion at some polymer concentration, resulting into nanoparticle aggregation and two-phase system. Further addition of polymer increases the polymer-polymer repulsion which eventually reduces the strength of depletion and hence re-entrant phase behavior. The effects of varying electrolyte concentration on the phase behavior of nanoparticle-polymer system are understood in terms of modifications in nanoparticle-nanoparticle and polymer-polymer interactions. The nanoparticle aggregates in two-phase systems are found to have surface fractal morphology.

Polymer ultrapermeability from the inefficient packing of 2D chains

NASA Astrophysics Data System (ADS)

Rose, Ian; Bezzu, C. Grazia; Carta, Mariolino; Comesaña-Gándara, Bibiana; Lasseuguette, Elsa; Ferrari, M. Chiara; Bernardo, Paola; Clarizia, Gabriele; Fuoco, Alessio; Jansen, Johannes C.; Hart, Kyle E.; Liyana-Arachchi, Thilanga P.; Colina, Coray M.; McKeown, Neil B.

2017-09-01

The promise of ultrapermeable polymers, such as poly(trimethylsilylpropyne) (PTMSP), for reducing the size and increasing the efficiency of membranes for gas separations remains unfulfilled due to their poor selectivity. We report an ultrapermeable polymer of intrinsic microporosity (PIM-TMN-Trip) that is substantially more selective than PTMSP. From molecular simulations and experimental measurement we find that the inefficient packing of the two-dimensional (2D) chains of PIM-TMN-Trip generates a high concentration of both small (<0.7 nm) and large (0.7-1.0 nm) micropores, the former enhancing selectivity and the latter permeability. Gas permeability data for PIM-TMN-Trip surpass the 2008 Robeson upper bounds for O2/N2, H2/N2, CO2/N2, H2/CH4 and CO2/CH4, with the potential for biogas purification and carbon capture demonstrated for relevant gas mixtures. Comparisons between PIM-TMN-Trip and structurally similar polymers with three-dimensional (3D) contorted chains confirm that its additional intrinsic microporosity is generated from the awkward packing of its 2D polymer chains in a 3D amorphous solid. This strategy of shape-directed packing of chains of microporous polymers may be applied to other rigid polymers for gas separations.

Formation of Nanofibrous Matrices, Three-Dimensional Scaffolds, and Microspheres: From Theory to Practice

PubMed Central

Ma, Chi

2017-01-01

Nanofibrous architecture presents unique biophysical cues to facilitate cellular responses and is considered an indispensable feature of a biomimetic three-dimensional (3D) scaffold and cell carrier. While electrospinning is a widely used method to prepare natural extracellular matrix-like nanofibers, it faces significant challenges to incorporate nanofibrous architecture into well-defined macroporous 3D scaffolds or injectable microspheres. Here we report a nonelectrospinning approach that is effective at generating nanofibers from a variety of synthetic and natural biodegradable polymers and integrating these nanofibers into (1) 3D scaffolds with constructive geometry and designed internal macropore structures; and (2) injectable microspheres. Our approach to generating polymer nanofibers is based on the control of polymer–solvent interaction parameter χp-s. We obtained the χp-s and solvent composition phase diagrams of different temperatures according to the Flory–Huggins classic lattice model and the Hildebrand-Scott solubility parameter equation. A critical polymer–solvent interaction parameter χcrit was introduced as a criterion to predict phase separation and nanofiber formation. To test the effectiveness of our approach, a total of 15 widely used biodegradable polymers were selected and successfully fabricated into nanofibrous matrices. Furthermore, macroporous nanofibrous 3D scaffolds with complex architecture and nanofibrous injectable microspheres were generated from those biodegradable polymers by combining our method with other processes. Our approach is universally effective to fabricate nanofibrous matrices from any polymeric materials. This work, therefore, greatly expands our ability to design appropriate biomimetic 3D scaffolds and injectable cell carriers for advanced regenerative therapies. PMID:27923327

Effect of ionic activity products on the structure and composition of mineral self assembled on three-dimensional poly(lactide-co-glycolide) scaffolds

PubMed Central

Shin, Kyungsup; Jayasuriya, Ambalangodage C.; Kohn, David H.

2009-01-01

A biomimetic approach involving the self-assembly of mineral within the pores of three-dimensional porous polymer scaffolds is a promising strategy to integrate advantages of inorganic and organic phases into a single material for hard tissue engineering. Such a material enhances the ability of progenitor cells to differentiate down an osteoblast lineage in vitro and in vivo, compared with polymer scaffolds. The mechanisms regulating mineral formation in this one-step process, however, are poorly understood, especially the effects of ionic activity products (IP) of the mineralizing solution and incubation time. The aims of this study were to define the structure and composition of mineral formed within the pores of biodegradable polymer scaffolds as a function of IP and time. Three-dimensional poly(lactide-co-glycolide) scaffolds were fabricated by solvent casting/particulate leaching and incubated for 4–16 days in six variants of simulated body fluid whose IPs were varied by adjusting ionic concentrations. Scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy demonstrated the formation of carbonated apatite with sub-micrometer sized crystals that grew into spherical globules extending out of the scaffold pore surfaces. As IP increased, more mineral grew on the scaffold pore surfaces, but the apatite became less crystalline and the Ca/P molar ratio decreased from 1.63 ± 0.005 to 1.51 ± 0.002. Since morphology, composition, and structure of mineral are factors that affect cell function, this study demonstrates that the IP of the mineralizing solution is an important modulator of material properties, potentially leading to enhanced control of cell function. PMID:17584901

Neighbor effect in complexation of a conjugated polymer.

PubMed

Sosorev, Andrey; Zapunidi, Sergey

2013-09-19

Charge-transfer complex (CTC) formation between a conjugated polymer and low-molecular-weight organic acceptor is proposed to be driven by the neighbor effect. Formation of a CTC on the polymer chain results in an increased probability of new CTC formation near the existing one. We present an analytical model for CTC distribution considering the neighbor effect, based on the principles of statistical mechanics. This model explains the experimentally observed threshold-like dependence of the CTC concentration on the acceptor content in a polymer:acceptor blend. It also allows us to evaluate binding energies of the complexes.

Topology Optimization of Lightweight Lattice Structural Composites Inspired by Cuttlefish Bone

NASA Astrophysics Data System (ADS)

Hu, Zhong; Gadipudi, Varun Kumar; Salem, David R.

2018-03-01

Lattice structural composites are of great interest to various industries where lightweight multifunctionality is important, especially aerospace. However, strong coupling among the composition, microstructure, porous topology, and fabrication of such materials impedes conventional trial-and-error experimental development. In this work, a discontinuous carbon fiber reinforced polymer matrix composite was adopted for structural design. A reliable and robust design approach for developing lightweight multifunctional lattice structural composites was proposed, inspired by biomimetics and based on topology optimization. Three-dimensional periodic lattice blocks were initially designed, inspired by the cuttlefish bone microstructure. The topologies of the three-dimensional periodic blocks were further optimized by computer modeling, and the mechanical properties of the topology optimized lightweight lattice structures were characterized by computer modeling. The lattice structures with optimal performance were identified.

A two-dimensional DNA lattice implanted polymer solar cell.

PubMed

Lee, Keun Woo; Kim, Kyung Min; Lee, Junwye; Amin, Rashid; Kim, Byeonghoon; Park, Sung Kye; Lee, Seok Kiu; Park, Sung Ha; Kim, Hyun Jae

2011-09-16

A double crossover tile based artificial two-dimensional (2D) DNA lattice was fabricated and the dry-wet method was introduced to recover an original DNA lattice structure in order to deposit DNA lattices safely on the organic layer without damaging the layer. The DNA lattice was then employed as an electron blocking layer in a polymer solar cell causing an increase of about 10% up to 160% in the power conversion efficiency. Consequently, the resulting solar cell which had an artificial 2D DNA blocking layer showed a significant enhancement in power conversion efficiency compared to conventional polymer solar cells. It should be clear that the artificial DNA nanostructure holds unique physical properties that are extremely attractive for various energy-related and photonic applications.

Benchtop fabrication of three-dimensional reconfigurable microfluidic devices from paper-polymer composite.

PubMed

Han, Yu Long; Wang, Wenqi; Hu, Jie; Huang, Guoyou; Wang, Shuqi; Lee, Won Gu; Lu, Tian Jian; Xu, Feng

2013-12-21

We presented a benchtop technique that can fabricate reconfigurable, three-dimensional (3D) microfluidic devices made from a soft paper-polymer composite. This fabrication approach can produce microchannels at a minimal width of 100 μm and can be used to prototype 3D microfluidic devices by simple bending and stretching. The entire fabrication process can be finished in 2 hours on a laboratory bench without the need for special equipment involved in lithography. Various functional microfluidic devices (e.g., droplet generator and reconfigurable electronic circuit) were prepared using this paper-polymer hybrid microfluidic system. The developed method can be applied in a wide range of standard applications and emerging technologies such as liquid-phase electronics.

Polymer photonic crystal slab waveguides

NASA Astrophysics Data System (ADS)

Liguda, C.; Böttger, G.; Kuligk, A.; Blum, R.; Eich, M.; Roth, H.; Kunert, J.; Morgenroth, W.; Elsner, H.; Meyer, H. G.

2001-04-01

We present details of the fabrication, calculations, and transmission measurements for finite two-dimensional (2D) polymer photonic crystal (PC) slab waveguides, which were fabricated from a benzocyclobutene polymer on a low refractive index substrate from Teflon. A square air hole lattice (500 nm lattice constant, 300 nm hole diameter) was realized by electron beam lithography and reactive ion etching. Polarization and wavelength dependent transmission results show TE-like and TM-like stop gaps at 1.3 μm excitation wavelengths and are in good agreement with the calculated data obtained by 2D and three-dimensional finite difference time domain methods. Transmission was suppressed by 15 dB in the center of the TE-like stop gap for a PC length of ten lattice constants.

Current status of one- and two-dimensional numerical models: Successes and limitations

NASA Technical Reports Server (NTRS)

Schwartz, R. J.; Gray, J. L.; Lundstrom, M. S.

1985-01-01

The capabilities of one and two-dimensional numerical solar cell modeling programs (SCAP1D and SCAP2D) are described. The occasions when a two-dimensional model is required are discussed. The application of the models to design, analysis, and prediction are presented along with a discussion of problem areas for solar cell modeling.

Emerging Insights into Directed Assembly: Taking Examples from Nature to Design Synthetic Processes

NASA Astrophysics Data System (ADS)

de Pablo, Juan J.

There is considerable interest in controlling the assembly of polymeric material in order to create highly ordered materials for applications. Such materials are often trapped in metastable, non-equilibrium states, and the processes through which they assemble become an important aspect of the materials design strategy. An example is provided by di-block copolymer directed self-assembly, where a decade of work has shown that, through careful choice of process variables, it is possible to create ordered structures whose degree of perfection meets the constraints of commercial semiconductor manufacturing. As impactful as that work has been, it has focused on relatively simple materials neutral polymers, consisting of two or at most three blocks. Furthermore, the samples that have been produced have been limited to relatively thin films, and the assembly has been carried out on ideal, two-dimensional substrates. The question that arises now is whether one can translate those achievements to polymeric materials having a richer sequence, to monomers that include charges, to three-dimensional substrates, or to active systems that are in a permanent non-equilibrium state. Building on discoveries from the biophysics literature, this presentation will review recent work from our group and others that explains how nature has evolved to direct the assembly of nucleic acids into intricate, fully three-dimensional macroscopic functional materials that are not only active, but also responsive to external cues. We will discuss how principles from polymer physics serve to explain those assemblies, and how one might design a new generation of synthetic systems that incorporate some of those principles.

Monte Carlo Computational Modeling of Atomic Oxygen Interactions

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Stueber, Thomas J.; Miller, Sharon K.; De Groh, Kim K.

2017-01-01

Computational modeling of the erosion of polymers caused by atomic oxygen in low Earth orbit (LEO) is useful for determining areas of concern for spacecraft environment durability. Successful modeling requires that the characteristics of the environment such as atomic oxygen energy distribution, flux, and angular distribution be properly represented in the model. Thus whether the atomic oxygen is arriving normal to or inclined to a surface and whether it arrives in a consistent direction or is sweeping across the surface such as in the case of polymeric solar array blankets is important to determine durability. When atomic oxygen impacts a polymer surface it can react removing a certain volume per incident atom (called the erosion yield), recombine, or be ejected as an active oxygen atom to potentially either react with other polymer atoms or exit into space. Scattered atoms can also have a lower energy as a result of partial or total thermal accommodation. Many solutions to polymer durability in LEO involve protective thin films of metal oxides such as SiO2 to prevent atomic oxygen erosion. Such protective films also have their own interaction characteristics. A Monte Carlo computational model has been developed which takes into account the various types of atomic oxygen arrival and how it reacts with a representative polymer (polyimide Kapton H) and how it reacts at defect sites in an oxide protective coating, such as SiO2 on that polymer. Although this model was initially intended to determine atomic oxygen erosion behavior at defect sites for the International Space Station solar arrays, it has been used to predict atomic oxygen erosion or oxidation behavior on many other spacecraft components including erosion of polymeric joints, durability of solar array blanket box covers, and scattering of atomic oxygen into telescopes and microwave cavities where oxidation of critical component surfaces can take place. The computational model is a two dimensional model which has the capability to tune the interactions of how the atomic oxygen reacts, scatters, or recombines on polymer or nonreactive surfaces. In addition to the specification of atomic oxygen arrival details, a total of 15 atomic oxygen interaction parameters have been identified as necessary to properly simulate observed interactions and resulting polymer erosion that have been observed in LEO. The tuning of the Monte Carlo model has been accomplished by adjusting interaction parameters so the erosion patterns produced by the model match those from several actual LEO space experiments. Surface texturing in LEO can also be predicted by the model. Such comparison of space tests with ground laboratory experiments have enabled confidence in ground laboratory lifetime prediction of protected polymers. Results of Monte Carlo tuning, examples of surface texturing and undercutting erosion prediction, and several examples of how the model can be used to predict other LEO and Mars orbital space results are presented.

A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

PubMed

Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

2015-06-01

The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

Macrocyclic {3d-4f} SMMs as building blocks for 1D-polymers: selective bridging of 4f ions by use of an O-donor ligand.

PubMed

Dhers, Sébastien; Feltham, Humphrey L C; Rouzières, Mathieu; Clérac, Rodolphe; Brooker, Sally

2016-11-15

Crystallisation of the tetranuclear 3d-4f Single-Molecule Magnet (SMM) [CuTb III (L Et )(NO 3 ) 3 (MeOH)]·MeOH (1) with Na 2 [tpa] (tpa = terephthalate and H 6 L Et is the [3 + 3] imine macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene and 1,2-diaminoethane) gives a structurally characterised one-dimensional cationic polymer {[CuTb III (L Et )(tpa)(H 2 O) 3 ](NO 3 )·0.5H 2 O·0.25MeOH} n (2). A comparative study of the static and dynamic magnetic properties of 2 and its precursor, 1, is reported.

Influence of test configuration on the combustion characteristics of polymers as ignition sources

NASA Technical Reports Server (NTRS)

Julien, Howard L.

1993-01-01

The experimental evaluation of polymers as ignition sources for metals was accomplished at the NASA White Sands Test Facility (WSTF) using a standard promoted combustion test. These tests involve the transient burning of materials in high-pressure oxygen environments. They have provided data from which design decisions can be made; data include video recordings of ignition and non-ignition for specific combinations of metals and polymers. Other tests provide the measured compositions of combustion products for polymers at select burn times and an empirical basis for estimating burn rates. With the current test configuration, the detailed analysis of test results requires modeling a three-dimensional, transient convection process involving fluid motion, thermal conduction and convection, the diffusion of chemical species, and the erosion of sample surface. At the high pressure extremes, it even requires the analysis of turbulent, transient convection where the physics of the problem are not well known and the computation requirements are not practical at this time. An alternative test configuration that can be analyzed with a relatively-simple convection model was developed during the summer period. The principal change constitutes replacing a large-diameter polymer disk at the end of the metal test rod with coaxial polymer cylinders that have a diameter nearer to that of the metal rod. The experimental objective is to assess the importance of test geometries on the promotion of metal ignition by testing with different lengths of the polymer and, with an extended effort, to analyze the surface combustion in the redesigned promoted combustion tests through analytical modeling of the process. The analysis shall use the results of cone-calorimeter tests of the polymer material to model primary chemical reactions and, with proper design of the promoted combustion test, modeling of the convection process could be conveniently limited to a quasi-steady boundary layer analysis where the economical solution of parabolic equations is involved. The products for the summer period are: (1) a conceptual-level redesign of the test apparatus, and (2) the development and use of an approximate integral boundary layer analysis to demonstrate the influence of geometry changes prior to testing. A computer code STAN5, an accurate numerical boundary layer model whose earlier versions were developed for the NASA Lewis Research Center by the Fellow, also was installed and validated on the WSTF and New Mexico State University computer systems as a starting point in the development of a more detailed fluid mechanics and combustion model.

Step-Growth Polymerization.

ERIC Educational Resources Information Center

Stille, J. K.

1981-01-01

Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

Three-Dimensional-Moldable Nanofiber-Reinforced Transparent Composites with a Hierarchically Self-Assembled "Reverse" Nacre-like Architecture.

PubMed

Biswas, Subir K; Sano, Hironari; Shams, Md Iftekhar; Yano, Hiroyuki

2017-09-06

Achieving a structural hierarchy and a uniform nanofiller dispersion simultaneously remains highly challenging for obtaining a robust polymer nanocomposite of immiscible components. In this study, a remarkably facile Pickering emulsification approach is developed to fabricate hierarchical composites of immiscible acrylic polymer and native cellulose nanofibers by taking advantage of the dual role of the nanofibers as both emulsion stabilizer and polymer reinforcement. The composites feature a unique "reverse" nacre-like microstructure reinforced with a well-dispersed two-tier hierarchical nanofiber network, leading to a synergistic high strength, modulus, and toughness (20, 50, and 53 times that of neat polymer, respectively), high optical transparency (89%), high flexibility, and a drastically low thermal expansion (13 ppm K -1 , 1/15th of the neat polymer). The nanocomposites have a three-dimensional-shape moldability, also their surface can be patterned with micro/nanoscale features with high fidelity by in situ compression molding, making them attractive as the substrate for flexible displays, smart contact lens devices, and photovoltaics. The Pickering emulsification approach should be broadly applicable for the fabrication of novel functional materials of various immiscible components.

Thermoreversible Folding as a Route to the Unique Shape-Memory Character in Ductile Polymer Networks.

PubMed

McBride, Matthew K; Podgorski, Maciej; Chatani, Shunsuke; Worrell, Brady T; Bowman, Christopher N

2018-06-21

Ductile, cross-linked films were folded as a means to program temporary shapes without the need for complex heating cycles or specialized equipment. Certain cross-linked polymer networks, formed here with the thiol-isocyanate reaction, possessed the ability to be pseudoplastically deformed below the glass transition, and the original shape was recovered during heating through the glass transition. To circumvent the large forces required to plastically deform a glassy polymer network, we have utilized folding, which localizes the deformation in small creases, and achieved large dimensional changes with simple programming procedures. In addition to dimension changes, three-dimensional objects such as swans and airplanes were developed to demonstrate applying origami principles to shape memory. We explored the fundamental mechanical properties that are required to fold polymer sheets and observed that a yield point that does not correspond to catastrophic failure is required. Unfolding occurred during heating through the glass transition, indicating the vitrification of the network that maintained the temporary, folded shape. Folding was demonstrated as a powerful tool to simply and effectively program ductile shape-memory polymers without the need for thermal cycling.

Room temperature rubbing for few-layer two-dimensional thin flakes directly on flexible polymer substrates

PubMed Central

Yu, Yan; Jiang, Shenglin; Zhou, Wenli; Miao, Xiangshui; Zeng, Yike; Zhang, Guangzu; Liu, Sisi

2013-01-01

The functional layers of few-layer two-dimensional (2-D) thin flakes on flexible polymers for stretchable applications have attracted much interest. However, most fabrication methods are “indirect” processes that require transfer steps. Moreover, previously reported “transfer-free” methods are only suitable for graphene and not for other few-layer 2-D thin flakes. Here, a friction based room temperature rubbing method is proposed for fabricating different types of few-layer 2-D thin flakes (graphene, hexagonal boron nitride (h-BN), molybdenum disulphide (MoS2), and tungsten disulphide (WS2)) on flexible polymer substrates. Commercial 2-D raw materials (graphite, h-BN, MoS2, and WS2) that contain thousands of atom layers were used. After several minutes, different types of few-layer 2-D thin flakes were fabricated directly on the flexible polymer substrates by rubbing procedures at room temperature and without any transfer step. These few-layer 2-D thin flakes strongly adhere to the flexible polymer substrates. This strong adhesion is beneficial for future applications. PMID:24045289

Orientational alignment in solids from bidimensional isotropic-anisotropic nuclear magnetic resonance spectroscopy: applications to the analysis of aramide fibers.

PubMed

Sachleben, J R; Frydman, L

1997-02-01

The use of two-dimensional isotropic-anisotropic correlation spectroscopy for the analysis of orientational alignment in solids is presented. The theoretical background and advantages of this natural-abundance 13C NMR method of measurement are discussed, and demonstrated with a series of powder and single-crystal variable-angle correlation spectroscopy (VACSY) experiments on model systems. The technique is subsequently employed to analyze the orientational distributions of three polymer fibers: Kevlar 29, Kevlar 49 and Kevlar 149. Using complementary two-dimensional NMR data recorded on synthetic samples of poly(p-phenyleneterephthalamide), the precursor of Kevlar, it was found that these commercial fibers possess molecules distributed over a very narrow orientational range with respect to the macroscopic director. The widths measured for these director distribution arrangements were (12 +/- 1.5) degrees for Kevlar 29, (15 +/- 1.5) degrees for Kevlar 49, and (8 +/- 1.5) degrees for Kevlar 149. These figures compare well with previous results obtained for non-commercial fiber samples derived from the same polymer.

Nanoparticle mediated micromotor motion

NASA Astrophysics Data System (ADS)

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

2015-03-01

In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ~200 μm s-1. By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ~10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems.In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ~200 μm s-1. By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ~10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems. Electronic supplementary information (ESI) available: Fig. S1-S5 and Video S1-S3. See DOI: 10.1039/c4nr07558g

Mechanically Strong, Polymer Cross-linked Aerogels (X-Aerogels)

NASA Technical Reports Server (NTRS)

Leventis, Nicholas

2006-01-01

Aerogels comprise a class of low-density, high porous solid objects consisting of dimensionally quasi-stable self-supported three-dimensional assemblies of nanoparticles. Aerogels are pursued because of properties above and beyond those of the individual nanoparticles, including low thermal conductivity, low dielectric constant and high acoustic impedance. Possible applications include thermal and vibration insulation, dielectrics for fast electronics, and hosting of functional guests for a wide variety of optical, chemical and electronic applications. Aerogels, however, are extremely fragile materials, hence they have found only limited application in some very specialized environments, for example as Cerenkov radiation detectors in certain types of nuclear reactors, aboard spacecraft as collectors of hypervelocity particles (refer to NASA's Stardust program) and as thermal insulators on planetary vehicles on Mars (refer to Sojourner Rover in 1997 and Spirit and Opportunity in 2004). Along these lines, the X-Aerogel is a new NASA-developed strong lightweight material that has resolved the fragility problem of traditional (native) aerogels. X-Aerogels are made by applying a conformal polymer coating on the surfaces of the skeletal nanoparticles of native aerogels (see Scanning Electron Micrographs). Since the relative amounts of the polymeric crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by the templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by remplated casting of polymer on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralighweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the the thermal conductivity of styrofoam. X-Aerogels have been demonstrated with several polymers such as polyurethanes/polyureas, epoxies and polyolefins, while crosslinking of approximately 35 different oxide aerogels yields a range of dimensionally stable, porous lightweight materials with unique combinations of structural, magnetic and optical properties. The main theme in materials development for space exploration is multifunction. For example, use of one material for thermal insulation/structural component will free weight for useful payload. In that regard, X-aerogels are evaluated at NASA for cryogenic fuel storage tanks and for spacesuits. Along the same lines, major impact fro X-Aerogels is also expected in commercial applications for thermal/acoustic insulation, in catalytic reformers and converters, in filtration membranes and membranes for fuel cells, as platforms for optical, electrical and magnetic sensors, and as lightweight structural component for aircraft and satellites.

Syntheses, crystal structures, and properties of four coordination polymers based on mixed multi-N donor and polycarboxylate ligands

NASA Astrophysics Data System (ADS)

Chen, Shui-Sheng; Guo, Xing-Zhe; Zhao, Yue; Li, Wei-Dong

2018-02-01

Four new coordination polymers [Ni2(HL1)2(L1)3(BTC)2]·6H2O (1), [Ni2(L1)3(HBTC)2]·4H2O (2), [Cd2(L2)(BTC)(H2O)3]·2H2O (3) and [Cd2(HL2)(BTCA)] (4) were synthesized by reactions of nickel(II)/ cadmium(II) salts with rigid ligands of 1,4-di(1H-imidazol-4-yl)benzene (L1), 1,3-di(1-imidazolyl)-5-(4H-tetrazol-5-yl)benzene (HL2) and polycarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. The complex 1 is one-dimensional (1D) chain while 2 is a (4, 4)-connected two-dimensional (2D) layered structure with 2D → 2D parallel interpenetration. Complex 3 is a rare tetranodal (3,4)-connected three-dimensional (3D) CrVTiSc architecture with Point (Schläfli) symbol of (4·82)(4·84·10)(42·82·102)(83), and compound 4 has the 2D network with (4,4) topology based on the [Cd2(COO)4] SBUs. The weak interactions such as hydrogen bonds and π···π stacking contribute to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. The UV-vis absorption spectra of 1 - 4 are discussed. Moreover, the photo luminescent properties of 3 and 4 and gas sorption property of 2 have been investigated.

Effect of interphase permittivity on the electric field distribution of epoxy nanocomposites

NASA Astrophysics Data System (ADS)

Pradeep, Lavanya; Nelson, Avinash; Preetha, P.

2018-05-01

Epoxy plays a vital role in high voltage insulation system due to its superior electrical and thermal properties. Literature reports the enhancement in these properties by the addition of nanofillers to epoxy and this enhancement is attributed to the effect of interphase. Characterization of polymer nanocomposites proves the importance of interphase formed between the polymer and nanoparticle in the composite. It was observed that the permittivity of the interphase is having a significant effect on the properties of these materials. In this work, a three dimensional Epoxy nanocomposite with 0.5 vol%, 1 vol% of alumina particles are modeled using unit cell approach in COMSOL Multiphysics. Simulation is done using several existing interphase permittivity models and field distribution is observed. Results shows the noticeable influence of interphase permittivity on the electric field distribution. A good correlation of electric field distribution with the AC breakdown strength is observed.

High Temperature Thermosets

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M.

1999-01-01

A thermoset or network polymer is an organic material where the molecules are tied together through chemical bonds (crosslinks) and therefore they cannot move past one another. As a result, these materials exhibit a certain degree of dimensional stability. The chemical composition and the degree of crosslink density of the thermoset have a pronounced effect upon the properties. High temperature thermosets offer a favorable combination of properties that makes them attractive for many applications. Their most important features are the excellent processability particularly of the low molecular weight precusor forms, the chemical and solvent resistance and the dimensional stability. The market for high temperature thermosets will increase as new uses for them are uncovered and new thermosets with better combinations of properties are developed.

Ion-Conducting Organic/Inorganic Polymers

NASA Technical Reports Server (NTRS)

Kinder, James D.; Meador, Mary Ann B.

2007-01-01

Ion-conducting polymers that are hybrids of organic and inorganic moieties and that are suitable for forming into solid-electrolyte membranes have been invented in an effort to improve upon the polymeric materials that have been used previously for such membranes. Examples of the prior materials include perfluorosulfonic acid-based formulations, polybenzimidazoles, sulfonated polyetherketone, sulfonated naphthalenic polyimides, and polyethylene oxide (PEO)-based formulations. Relative to the prior materials, the polymers of the present invention offer greater dimensional stability, greater ease of formation into mechanically resilient films, and acceptably high ionic conductivities over wider temperature ranges. Devices in which films made of these ion-conducting organic/inorganic polymers could be used include fuel cells, lithium batteries, chemical sensors, electrochemical capacitors, electrochromic windows and display devices, and analog memory devices. The synthesis of a polymer of this type (see Figure 1) starts with a reaction between an epoxide-functionalized alkoxysilane and a diamine. The product of this reaction is polymerized by hydrolysis and condensation of the alkoxysilane group, producing a molecular network that contains both organic and inorganic (silica) links. The silica in the network contributes to the ionic conductivity and to the desired thermal and mechanical properties. Examples of other diamines that have been used in the reaction sequence of Figure 1 are shown in Figure 2. One can use any of these diamines or any combination of them in proportions chosen to impart desired properties to the finished product. Alternatively or in addition, one could similarly vary the functionality of the alkoxysilane to obtain desired properties. The variety of available alkoxysilanes and diamines thus affords flexibility to optimize the organic/inorganic polymer for a given application.

Design and Synthesis of a Biocompatible 1D Coordination Polymer as Anti-Breast Cancer Drug Carrier, 5-Fu: In Vitro and in Vivo Studies.

PubMed

Rezaei, Mahsa; Abbasi, Alireza; Dinarvand, Rassoul; Jeddi-Tehrani, Mahmood; Janczak, Jan

2018-05-17

Designable coordination polymers with suitable chemical diversities and biocompatible structures have been proposed as a promising class of vehicles for drug delivery systems. Here, we hydrothermally synthesized a novel one-dimensional (1D) coordination polymer, [Zn(H 2 O) 6 K 2 (H 2 BTC) 2 (H 2 O) 4 ](H 2 BTC) 2 ·2H 2 O, where H 3 BTC = benzene-1,3,5-tricarboxylic acid (trimesic acid), cp.1. As the hydrogen bonds stabilized 1D chains in three dimensions, the cp.1 could be a good candidate for delivering small-molecule chemotherapeutics such as 5-fluorouracil (5-Fu). The synthesized cp.1 showed a remarkable 5-Fu loading of 66% with encapsulation efficiency of 98% and almost complete release process. The 5-Fu-loaded cp.1 displayed a time-dependent cytotoxicity effect against breast cancer cell lines MCF-7 and 4T1. The cellular uptake of cp.1 particles was investigated via confocal laser scanning microscopy using fluorescein isothiocyanate and LysoTracker Red staining. Furthermore, the in vivo antitumor impact of 5-Fu-loaded cp.1 was studied on 4T1 breast cancer BALB/c mice model. The intratumor treatment of 5-Fu-loaded cp.1 demonstrated beneficial antitumor efficacy by postponing tumor growth. These results suggest that the 5-Fu-loaded cp.1 microparticles with a great locoregional delivery can be efficient anticancer drug carriers for further clinical treatments.

Polymer Fluid Dynamics: Continuum and Molecular Approaches.

PubMed

Bird, R B; Giacomin, A J

2016-06-07

To solve problems in polymer fluid dynamics, one needs the equations of continuity, motion, and energy. The last two equations contain the stress tensor and the heat-flux vector for the material. There are two ways to formulate the stress tensor: (a) One can write a continuum expression for the stress tensor in terms of kinematic tensors, or (b) one can select a molecular model that represents the polymer molecule and then develop an expression for the stress tensor from kinetic theory. The advantage of the kinetic theory approach is that one gets information about the relation between the molecular structure of the polymers and the rheological properties. We restrict the discussion primarily to the simplest stress tensor expressions or constitutive equations containing from two to four adjustable parameters, although we do indicate how these formulations may be extended to give more complicated expressions. We also explore how these simplest expressions are recovered as special cases of a more general framework, the Oldroyd 8-constant model. Studying the simplest models allows us to discover which types of empiricisms or molecular models seem to be worth investigating further. We also explore equivalences between continuum and molecular approaches. We restrict the discussion to several types of simple flows, such as shearing flows and extensional flows, which are of greatest importance in industrial operations. Furthermore, if these simple flows cannot be well described by continuum or molecular models, then it is not necessary to lavish time and energy to apply them to more complex flow problems.

Ultra-compact laser beam steering device using holographically formed two dimensional photonic crystal.

PubMed

Dou, Xinyuan; Chen, Xiaonan; Chen, Maggie Yihong; Wang, Alan Xiaolong; Jiang, Wei; Chen, Ray T

2010-03-01

In this paper, we report the theoretical study of polymer-based photonic crystals for laser beam steering which is based on the superprism effect as well as the experiment fabrication of the two dimensional photonic crystals for the laser beam steering. Superprism effect, the principle for beam steering, was separately studied in details through EFC (Equifrequency Contour) analysis. Polymer based photonic crystals were fabricated through double exposure holographic interference method using SU8-2007. The experiment results showed a beam steering angle of 10 degree for 30 nm wavelength variation.

Separation of Arylenevinylene Macrocycles with a Surface-Confined Two-Dimensional Covalent Organic Framework.

PubMed

Liu, Chunhua; Park, Eunsol; Jin, Yinghua; Liu, Jie; Yu, Yanxia; Zhang, Wei; Lei, Shengbin; Hu, Wenping

2018-05-31

A two-dimensional surface covalent organic framework, prepared by a surface-confined synthesis using 4,4'-azodianiline and benzene-1,3,5-tricarbaldehyde as the precursors, was used as a host network to effectively immobilize arylenevinylene macrocycles (AVMs). Thus AVMs could be separated from their linear polymer analogues, which are the common side-products in the cyclooligomerization process. Scanning tunneling microscopy investigations revealed efficient removal of linear polymers by a simple surface binding and solvent washing process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Swelling of two-dimensional polymer rings by trapped particles.

PubMed

Haleva, E; Diamant, H

2006-09-01

The mean area of a two-dimensional Gaussian ring of N monomers is known to diverge when the ring is subject to a critical pressure differential, p c ~ N -1. In a recent publication (Eur. Phys. J. E 19, 461 (2006)) we have shown that for an inextensible freely jointed ring this divergence turns into a second-order transition from a crumpled state, where the mean area scales as [A]~N-1, to a smooth state with [A]~N(2). In the current work we extend these two models to the case where the swelling of the ring is caused by trapped ideal-gas particles. The Gaussian model is solved exactly, and the freely jointed one is treated using a Flory argument, mean-field theory, and Monte Carlo simulations. For a fixed number Q of trapped particles the criticality disappears in both models through an unusual mechanism, arising from the absence of an area constraint. In the Gaussian case the ring swells to such a mean area, [A]~ NQ, that the pressure exerted by the particles is at p c for any Q. In the freely jointed model the mean area is such that the particle pressure is always higher than p c, and [A] consequently follows a single scaling law, [A]~N(2) f (Q/N), for any Q. By contrast, when the particles are in contact with a reservoir of fixed chemical potential, the criticality is retained. Thus, the two ensembles are manifestly inequivalent in these systems.

Modeling of laser transmission contour welding process using FEA and DoE

NASA Astrophysics Data System (ADS)

Acherjee, Bappa; Kuar, Arunanshu S.; Mitra, Souren; Misra, Dipten

2012-07-01

In this research, a systematic investigation on laser transmission contour welding process is carried out using finite element analysis (FEA) and design of experiments (DoE) techniques. First of all, a three-dimensional thermal model is developed to simulate the laser transmission contour welding process with a moving heat source. The commercial finite element code ANSYS® multi-physics is used to obtain the numerical results by implementing a volumetric Gaussian heat source, and combined convection-radiation boundary conditions. Design of experiments together with regression analysis is then employed to plan the experiments and to develop mathematical models based on simulation results. Four key process parameters, namely power, welding speed, beam diameter, and carbon black content in absorbing polymer, are considered as independent variables, while maximum temperature at weld interface, weld width, and weld depths in transparent and absorbing polymers are considered as dependent variables. Sensitivity analysis is performed to determine how different values of an independent variable affect a particular dependent variable.

Quantitative structure-activity relationships for green algae growth inhibition by polymer particles.

PubMed

Nolte, Tom M; Peijnenburg, Willie J G M; Hendriks, A Jan; van de Meent, Dik

2017-07-01

After use and disposal of chemical products, many types of polymer particles end up in the aquatic environment with potential toxic effects to primary producers like green algae. In this study, we have developed Quantitative Structure-Activity Relationships (QSARs) for a set of highly structural diverse polymers which are capable to estimate green algae growth inhibition (EC50). The model (N = 43, R 2  = 0.73, RMSE = 0.28) is a regression-based decision tree using one structural descriptor for each of three polymer classes separated based on charge. The QSAR is applicable to linear homo polymers as well as copolymers and does not require information on the size of the polymer particle or underlying core material. Highly branched polymers, non-nitrogen cationic polymers and polymeric surfactants are not included in the model and thus cannot be evaluated. The model works best for cationic and non-ionic polymers for which cellular adsorption, disruption of the cell wall and photosynthesis inhibition were the mechanisms of action. For anionic polymers, specific properties of the polymer and test characteristics need to be known for detailed assessment. The data and QSAR results for anionic polymers, when combined with molecular dynamics simulations indicated that nutrient depletion is likely the dominant mode of toxicity. Nutrient depletion in turn, is determined by the non-linear interplay between polymer charge density and backbone flexibility. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of the Three-Dimensional Vector FAÇADE Model Created from Photogrammetric Data

NASA Astrophysics Data System (ADS)

Kamnev, I. S.; Seredovich, V. A.

2017-12-01

The results of the accuracy assessment analysis for creation of a three-dimensional vector model of building façade are described. In the framework of the analysis, analytical comparison of three-dimensional vector façade models created by photogrammetric and terrestrial laser scanning data has been done. The three-dimensional model built from TLS point clouds was taken as the reference one. In the course of the experiment, the three-dimensional model to be analyzed was superimposed on the reference one, the coordinates were measured and deviations between the same model points were determined. The accuracy estimation of the three-dimensional model obtained by using non-metric digital camera images was carried out. Identified façade surface areas with the maximum deviations were revealed.

Low Loss Graded Index Polymer Optical Fiber for Local Networking

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

Claus, Richard Otto

The objective of this Department of Energy SBIR program has been to develop technology for the advancement of advanced computing systems. NanoSonic worked with two subcontractors, the Polymicro Division of Molex, a U.S.-based manufacturer of specialized optical fiber and fiber components, and Virginia Tech, a research university involved through the Global Environment for Network Innovations (GENI) program in high-speed computer networking research. NanoSonic developed a patented molecular-level self-assembly process to manufacture polymer-based optical fibers in a way similar to the modified chemical vapor deposition (MCVD) approach typically used to make glass optical fibers. Although polymer fiber has a higher attenuationmore » per unit length than glass fiber, short connectorized polymer fiber jumpers offer significant cost savings over their glass counterparts, particularly due to the potential use of low-cost plastic fiber connectors. As part of the SBIR commercialization process, NanoSonic exclusively licensed this technology to a large ($100B+ market cap) U.S.-based manufacturing conglomerate near the end of the first year of the Phase II program. With this base technology developed and licensed, NanoSonic then worked with Polymicro to address secondary program goals of using related but not conflicting production methods to enhance the performance of other specialty optical fiber products and components, and Virginia Tech continued its evaluation of developed polymer fibers in its network infrastructure system on the university campus. We also report our current understanding of the observation during the Phase I program of quantum conductance and partial quantum conductance in metal-insulator-metal (MIM) devices. Such conductance behavior may be modeled as singlemode behavior in one-dimensional electrically conducting waveguides, similar in principle to singlemode optical propagation in dielectric fiber waveguides. Although NanoSonic has not licensed any of the additional technology developed during the second year of the program, several proprietary discussions with major materials companies are underway as of the conclusion of Phase II.« less

Residual thermal stresses in composites for dimensionally stable spacecraft applications

NASA Technical Reports Server (NTRS)

Bowles, David E.; Tompkins, Stephen S.; Funk, Joan G.

1992-01-01

An overview of NASA LaRC's research on thermal residual stresses and their effect on the dimensional stability of carbon fiber reinforced polymer-matrix composites is presented. The data show that thermal residual stresses can induce damage in polymer matrix composites and significantly affect the dimensional stability of these composites by causing permanent residual strains and changes in CTE. The magnitude of these stresses is primarily controlled by the laminate configuration and the applied temperature change. The damage caused by thermal residual stresses initiates at the fiber/matrix interface and micromechanics level analyses are needed to accurately predict it. An increased understanding of fiber/matrix interface interactions appears to be the best approach for improving a composite's resistance to thermally induced damage.

Fit of interim crowns fabricated using photopolymer-jetting 3D printing.

PubMed

Mai, Hang-Nga; Lee, Kyu-Bok; Lee, Du-Hyeong

2017-08-01

The fit of interim crowns fabricated using 3-dimensional (3D) printing is unknown. The purpose of this in vitro study was to evaluate the fit of interim crowns fabricated using photopolymer-jetting 3D printing and to compare it with that of milling and compression molding methods. Twelve study models were fabricated by making an impression of a metal master model of the mandibular first molar. On each study model, interim crowns (N=36) were fabricated using compression molding (molding group, n=12), milling (milling group, n=12), and 3D polymer-jetting methods. The crowns were prepared as follows: molding group, overimpression technique; milling group, a 5-axis dental milling machine; and polymer-jetting group using a 3D printer. The fit of interim crowns was evaluated in the proximal, marginal, internal axial, and internal occlusal regions by using the image-superimposition and silicone-replica techniques. The Mann-Whitney U test and Kruskal-Wallis tests were used to compare the results among groups (α=.05). Compared with the molding group, the milling and polymer-jetting groups showed more accurate results in the proximal and marginal regions (P<.001). In the axial regions, even though the mean discrepancy was smallest in the molding group, the data showed large deviations. In the occlusal region, the polymer-jetting group was the most accurate, and compared with the other groups, the milling group showed larger internal discrepancies (P<.001). Polymer-jet 3D printing significantly enhanced the fit of interim crowns, particularly in the occlusal region. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Fabrication and characterization of poly(propylene fumarate) scaffolds with controlled pore structures using 3-dimensional printing and injection molding.

PubMed

Lee, Kee-Won; Wang, Shanfeng; Lu, Lichun; Jabbari, Esmaiel; Currier, Bradford L; Yaszemski, Michael J

2006-10-01

Poly(propylene fumarate) (PPF) is an injectable, biodegradable polymer that has been used for fabricating preformed scaffolds in tissue engineering applications because of in situ crosslinking characteristics. Aiming for understanding the effects of pore structure parameters on bone tissue ingrowth, 3-dimensional (3D) PPF scaffolds with controlled pore architecture have been produced in this study from computer-aided design (CAD) models. We have created original scaffold models with 3 pore sizes (300, 600, and 900 microm) and randomly closed 0%, 10%, 20%, or 30% of total pores from the original models in 3 planes. PPF scaffolds were fabricated by a series steps involving 3D printing of support/build constructs, dissolving build materials, injecting PPF, and dissolving support materials. To investigate the effects of controlled pore size and interconnectivity on scaffolds, we compared the porosities between the models and PPF scaffolds fabricated thereby, examined pore morphologies in surface and cross-section using scanning electron microscopy, and measured permeability using the falling head conductivity test. The thermal properties of the resulting scaffolds as well as uncrosslinked PPF were determined by differential scanning calorimetry and thermogravimetric analysis. Average pore sizes and pore shapes of PPF scaffolds with 600- and 900-microm pores were similar to those of CAD models, but they depended on directions in those with 300-microm pores. Porosity and permeability of PPF scaffolds decreased as the number of closed pores in original models increased, particularly when the pore size was 300 microm as the result of low porosity and pore occlusion. These results show that 3D printing and injection molding technique can be applied to crosslinkable polymers to fabricate 3D porous scaffolds with controlled pore structures, porosity, and permeability using their CAD models.

Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR) Methodology

PubMed Central

Wen, Jia-Long; Sun, Shao-Long; Xue, Bai-Liang; Sun, Run-Cang

2013-01-01

The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA), nitrobenzene oxidation (NBO), and derivatization followed by reductive cleavage (DFRC). Recent advances in nuclear magnetic resonance (NMR) technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ), as well as their applications are reviewed. PMID:28809313

Studies on the relation between the size and dispersion of metallic silver nanoparticles and morphologies of initial silver(I) coordination polymer precursor

NASA Astrophysics Data System (ADS)

Moradi, Zhaleh; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

2017-04-01

Micro and nano-structures of [Ag2(μ2-dcpa)2]n (1), [Hdcpa = 2,4-dichlorophenoxyacetic acid] which is a one-dimensional coordination polymer with corrugated tape chains, were synthesized as the bulk sample (1B), by sonochemical process (1S) and from mechanochemical reaction (1M). These three samples have been used as new precursors for fabricating silver nanoparticles via direct calcination at 300 °C and also thermal decomposition in oleic acid (OA) as a surfactant at 180 °C. In the presence of OA less agglomerated nanostructures were formed. It seems that the size, dispersion, morphology and agglomeration of initial precursor have direct influence on size, dispersion, morphology and agglomeration of metallic silver. This coordination polymer with various micro and nano morphologies were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stability of these samples were studied and compared with each other, too.

Polymer adsorption-driven self-assembly of nanostructures.

PubMed

Chakraborty, A K; Golumbfskie, A J

2001-01-01

Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context.

A new redox-active coordination polymer with cobalticinium dicarboxylate.

PubMed

Kondo, Mitsuru; Hayakawa, Yuri; Miyazawa, Makoto; Oyama, Aiko; Unoura, Kei; Kawaguchi, Hiroyuki; Naito, Tetsuyoshi; Maeda, Kenji; Uchida, Fumio

2004-09-20

A new two-dimensional coordination polymer with cobalticinium 1,1'-dicarboxylate (ccdc) incorporated in the framework has been prepared, the ccdc functioning as unique monoanionic dicarboxylate ligands. The compound shows a high redox activity based on the ccdc units. Copyright 2004 American Chemical Society

Influence of graphene quantum dots on electrical properties of polymer composites

NASA Astrophysics Data System (ADS)

Arthisree, D.; Joshi, Girish M.

2017-07-01

We successfully prepared synthetic nanocomposite (SNC) by dispersing graphene quantum dots (GQD) in cellulose acetate (CA) polymer system. The dispersion and occupied network of GQD were foreseen by microscopic techniques. The variation of plane to crossed linked array network was observed by the polarizing optical microscopic (POM) technique. The scanning electron microscopy (SEM) revealed the leaves like impressions of GQD in host polymer system. The series network of GQD occupied in CA at higher resolution was confirmed by transmission electron microscopy (TEM). The two dimensional (2D) topographic images demonstrated an entangled polymer network to plane morphology. The variation in surface roughness was evaluated from the dimensional (3D) topography. The influence of temperature on AC conductivity with highest value (4  ×  10-5 S cm-1), contributes to the decrease in activation energy. The DC conductivity obeys the percolation criteria co-related to the GQD loading by weight fraction. Furthermore, this synthetic nanocomposite is feasible for the development of sensing and electrical applications.

From Semi- to Full-Two-Dimensional Conjugated Side-Chain Design: A Way toward Comprehensive Solar Energy Absorption

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

Chao, Pengjie; Wang, Huan; Qu, Shiwei

Two polymers with fully two-dimensional (2D) conjugated side chains, 2D-PTB-Th and 2D-PTB-TTh, were synthesized and characterized through simultaneously integrating the 2D-TT and the 2D-BDT monomers onto the polymer backbone. Resulting from the synergistic effect from the conjugated side chains on both monomers, the two polymers showed remarkably efficient absorption of the sunlight and improved pi-pi intermolecular interactions for efficient charge carrier transport. The optimized bulk heterojunction device based on 2D-PTB-Th and PC71BM shows a higher PCE of 9.13% compared to PTB7-Th with a PCE of 8.26%, which corresponds to an approximately 10% improvement in solar energy conversion. The fully 2D-conjugatedmore » side-chain concept reported here developed a new molecular design strategy for polymer materials with enhanced sunlight absorption and efficient solar energy conversion.« less

Transient Stress Wave Propagation in One-Dimensional Micropolar Bodies

DTIC Science & Technology

2009-02-01

based on Biot’s theory of poro- elasticity. Two compressional waves were then observed in the resulting one-dimensional model of a poroelastic column...Lisina, S., Potapov, A., Nesterenko, V., 2001. A nonlinear granular medium with particle rotation: a one-dimensional model . Acoustical Physics 47 (5...zones in failed ceramics, may be modeled using continuum theories incorporating additional kinematic degrees of freedom beyond the scope of classical

All-Polymer Solar Cell Performance Optimized via Systematic Molecular Weight Tuning of Both Donor and Acceptor Polymers.

PubMed

Zhou, Nanjia; Dudnik, Alexander S; Li, Ting I N G; Manley, Eric F; Aldrich, Thomas J; Guo, Peijun; Liao, Hsueh-Chung; Chen, Zhihua; Chen, Lin X; Chang, Robert P H; Facchetti, Antonio; Olvera de la Cruz, Monica; Marks, Tobin J

2016-02-03

The influence of the number-average molecular weight (Mn) on the blend film morphology and photovoltaic performance of all-polymer solar cells (APSCs) fabricated with the donor polymer poly[5-(2-hexyldodecyl)-1,3-thieno[3,4-c]pyrrole-4,6-dione-alt-5,5-(2,5-bis(3-dodecylthiophen-2-yl)thiophene)] (PTPD3T) and acceptor polymer poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2); N2200) is systematically investigated. The Mn effect analysis of both PTPD3T and N2200 is enabled by implementing a polymerization strategy which produces conjugated polymers with tunable Mns. Experimental and coarse-grain modeling results reveal that systematic Mn variation greatly influences both intrachain and interchain interactions and ultimately the degree of phase separation and morphology evolution. Specifically, increasing Mn for both polymers shrinks blend film domain sizes and enhances donor-acceptor polymer-polymer interfacial areas, affording increased short-circuit current densities (Jsc). However, the greater disorder and intermixed feature proliferation accompanying increasing Mn promotes charge carrier recombination, reducing cell fill factors (FF). The optimized photoactive layers exhibit well-balanced exciton dissociation and charge transport characteristics, ultimately providing solar cells with a 2-fold PCE enhancement versus devices with nonoptimal Mns. Overall, it is shown that proper and precise tuning of both donor and acceptor polymer Mns is critical for optimizing APSC performance. In contrast to reports where maximum power conversion efficiencies (PCEs) are achieved for the highest Mns, the present two-dimensional Mn optimization matrix strategy locates a PCE "sweet spot" at intermediate Mns of both donor and acceptor polymers. This study provides synthetic methodologies to predictably access conjugated polymers with desired Mn and highlights the importance of optimizing Mn for both polymer components to realize the full potential of APSC performance.

A two-dimensional polymer synthesized at the air/water interface.

PubMed

Schlüter, A Dieter; Müller, Vivian; Hinaut, Antoine; Moradi, Mina; Baljozovic, Milos; Jung, Thomas; Shahgaldian, Patrick; Möhwald, Helmuth; Hofer, Gregor; Kröger, Martin; King, Benjamin; Meyer, Ernst; Glatzel, Thilo

2018-06-11

A trifunctional, partially fluorinated anthracene-substituted triptycene monomer is spread at the air/water interface into a monolayer, which is transformed into a long-range ordered 2D polymer by irradiation with a standard ultraviolet lamp using 365 nm light. The polymer is analyzed by Brewster angle microscopy directly at this interface and by scanning tunneling microscopy measurements and non-contact atomic force microscopy (nc-AFM), both after transfer from below the interface onto highly oriented pyrolytic graphite and then into ultra-high vacuum. Both methods confirm a network structure, the lattice parameters of which are virtually identical to a structural model network based on X-ray diffractometry of a closely related 2D polymer unequivocally established in a single crystal. The nc-AFM images are obtained with unprecedentedly high resolution and prove long-range order over areas of at least 300 × 300 nm2. As required for a 2D polymer, the pore sizes are monodisperse, except for the regions, where the network is somewhat stretched because it spans over protrusions. Together with a previous report on the nature of the cross-links in this network, the structural information provided here leaves no doubt that a 2D polymer has been synthesized under ambient conditions at an air/water interface. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Limit Properties of One Dimensional Periodic Hopping Model

NASA Astrophysics Data System (ADS)

Zhang, Yun-xin

2010-02-01

One dimensional periodic hopping model is useful to understand the motion of microscopic particles in thermal noise environment. In this research, by formal calculation and based on detailed balance, the explicit expressions of the limits of mean velocity and diffusion constant of this model as the number of internal mechanochemical sates tend to infinity are obtained. These results will be helpful to understand the limit of the one dimensional hopping model. At the same time, the work can be used to get more useful results in continuous form from the corresponding ones obtained by discrete models.

Glassy dynamics of polymethylphenylsiloxane in one- and two-dimensional nanometric confinement—A comparison

NASA Astrophysics Data System (ADS)

Kipnusu, Wycliffe K.; Elsayed, Mohamed; Krause-Rehberg, Reinhard; Kremer, Friedrich

2017-05-01

Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D) nanometric confinement; the former is realized in thin polymer layers having thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 μm) nanopores with diameters varying between 4 and 8 nm. Based on the dielectric measurements carried out in a broad spectral range at widely varying temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements with the following results: (i) the segmental dynamics (dynamic glass transition) of PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the mean relaxation rate and the width of the relaxation time distribution function; (ii) additionally a well separated surface induced relaxation is observed, being assigned to adsorption and desorption processes of polymer segments with the solid interface; (iii) in 2D confinement with native inner pore walls, the segmental dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the segmental dynamics; on silanization, this dependence on the pore diameter vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a 2D confinement, a pronounced surface induced relaxation process is found, the strength of which increases with the decreasing pore diameter; it can be fully removed by silanization of the inner pore walls; (v) the surface induced relaxation depends on its spectral position only negligibly on the pore diameter; (vi) comparing 1D and 2D confinements, the segmental dynamics in the latter is by about two orders of magnitude faster. All these findings can be comprehended by considering the density of the polymer; in 1D it is assumed to be the same as in the bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a frustration of packaging resulting in a higher free volume, as proven by ortho-positronium annihilation lifetime spectroscopy.

Controlled Interactions between Two Dimensional Layered Inorganic Nanosheets and Polymers

DTIC Science & Technology

2016-06-15

transition metal and non- pair electrons of amine allows us to develop scalable, stable and uniform composite films with numerous combinations of TMD...modification of TMDs sheets with amine-terminated polymers is introduced and the strong Lewis acid-base interaction between transition metal and non- pair ...can be readily entangled with other chains of the matrix polymer, thereby ensuring homogeneous PNC formation. The solvent medium offers an extra

An Overview on Additive Manufacturing of Polymers

NASA Astrophysics Data System (ADS)

Jasiuk, Iwona; Abueidda, Diab W.; Kozuch, Christopher; Pang, Siyuan; Su, Frances Y.; McKittrick, Joanna

2018-03-01

We present an overview on additive manufacturing (AM), also called three-dimensional printing, with a focus on polymers. First, we introduce the AM concept. Next, we outline several AM processes, including their advantages and limitations, and list common polymers that are used in commercial printers. Then, we state various AM applications and present two examples. We conclude with a global view of the AM field, its challenges, and future directions.

Characterization of Polymer Blends: Optical Microscopy (*Polarized, Interference and Phase Contrast Microscopy*) and Confocal Microscopy

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

Ramanathan, Nathan Muruganathan; Darling, Seth B.

2015-01-01

Chapter 15 surveys the characterization of macro, micro and meso morphologies of polymer blends by optical microscopy. Confocal Microscopy offers the ability to view the three dimensional morphology of polymer blends, popular in characterization of biological systems. Confocal microscopy uses point illumination and a spatial pinhole to eliminate out-of focus light in samples that are thicker than the focal plane.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G; Katsoulidis, Alexandros

2015-03-10

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G.; Katsoulidis, Alexandros

2016-10-18

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

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

A Functional Central Limit Theorem for the Becker-Döring Model

NASA Astrophysics Data System (ADS)

Sun, Wen

2018-04-01

We investigate the fluctuations of the stochastic Becker-Döring model of polymerization when the initial size of the system converges to infinity. A functional central limit problem is proved for the vector of the number of polymers of a given size. It is shown that the stochastic process associated to fluctuations is converging to the strong solution of an infinite dimensional stochastic differential equation (SDE) in a Hilbert space. We also prove that, at equilibrium, the solution of this SDE is a Gaussian process. The proofs are based on a specific representation of the evolution equations, the introduction of a convenient Hilbert space and several technical estimates to control the fluctuations, especially of the first coordinate which interacts with all components of the infinite dimensional vector representing the state of the process.

New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

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

Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning

Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu{sub 4}(fph){sub 2}(bpe){sub 3}(H{sub 2}O){sub 2}]·2H{sub 2}O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co{sub 2}(fph)(bpa){sub 2}(H{sub 2}O){sub 2}]·3H{sub 2}O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H{sub 2}O)(H{sub 2}oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu{sup 2+} ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. Formore » compound 2, the fph molecules still serve as the first connectors, linking the Co{sup 2+} ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated.« less

Effect of hydrogen peroxide on the three-dimensional polymer network in composites.

PubMed

Durner, Jürgen; Stojanovic, Marija; Urcan, Ebru; Spahl, Werner; Haertel, Ursula; Hickel, Reinhard; Reichl, Franx-Xaver

2011-06-01

Less data are available about the effects of hydrogen peroxide on the three-dimensional polymer network of polymerized composites. Therefore the study was performed to test the effects of hydrogen peroxide on the three-dimensional polymer network in composites. Polymerized specimens from Tetric Flow®, Tetric Ceram® and Filtek™ Supreme XT were bleached with Opalescence® PF 15% for 5h or PF 35% for 0.5h, respectively, and then stored in methanol for 1d and 7d. Controls were unbleached specimens. The eluates were analyzed by gas chromatography/mass spectrometry. More methacrylic acid (MAA), bisphenol-A (BPA), ethoxylated bisphenol-A-dimethacrylate (BisEMA), hydroquinone monomethyl ether (HQME), 1,10-decanediol dimethacrylate (DDDMA) and/or triethylene glycol dimethacrylate (TEGDMA) were eluted from bleached specimens compared with non bleached controls (1d). The highest DDDMA amount of 419.8 μmol/l was found in the eluates after 7d in Tetric Flow® specimens treated with PF 15. The highest HQME amount of 159.6 μmol/l was found in eluates from Tetric Ceram® specimens treated with PF after 7d. The highest TEGDMA amount of 178.7 μmol/l was found in eluates from Filtek™ Supreme XT specimens treated with PF 35 after 7d. Bleaching with hydrogen peroxide has an effect on the three-dimensional polymer network in polymerized composites leading to an increase in the release of unpolymerized monomers, additives and unspecific oxidative products. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Panoramic View of Electrochemical Pseudocapacitor and Organic Solar Cell Research in Molecularly Engineered Energy Materials (MEEM)

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

Aguirre, Jordan C.; Ferreira, Amy; Ding, Hong

2014-07-09

Our program on capacitive energy storage is a comprehensive one that combines experimental and computational components to achieve a fundamental understanding of charge storage processes in redox-based materials, specifically transition metal oxides. Some of the highlights of this program are the identification of intercalation pseudocapacitance in Nb2O5, which enables high energy density to be achieved at high rates, and the development of a new route for synthesizing mesoporous films in which preformed nanocrystal building blocks are used in combination with polymer templating. The resulting material architectures have large surface areas and enable electrolyte access to the redox active pore walls,more » while the interconnected mesoporous film provides good electronic conductivity. Select first-principles density-functional theory studies of prototypical pseudocapacitor materials are reviewed, providing insight into the key physical and chemical features involved in charge transfer and ion diffusion. Rigorous multiscale physical models and numerical tools have been developed and used to reproduce electrochemical properties of carbon-based electrochemical capacitors with the ultimate objective of facilitating the optimization of electrode design. For the organic photovoltaic (OPV) program, our focus has been ongoing beyond the trial-and-error Edisonian approaches that have been responsible for the increase in power conversion efficiency of blend-cast (BC) bulk heterojunction blends of polymers and fullerenes. Our first approach has been to use molecular self-assembly to create the ideal nanometer-scale architecture using thermodynamics rather than relying on the kinetics of spontaneous phase segregation. We have created fullerenes that self-assemble into one-dimensional stacks and have shown that use of these self-assembled fullerenes lead to dramatically enhanced OPV performance relative to fullerenes that do not assemble. We also have created self-assembling conjugated polymers that form gels based on electrically continuous cross-linked micelles in solution, opening the possibility for water-processable “green” production of OPVs based on these materials. Our second approach has been to avoid kinetic control over phase separation by using a sequential processing (SqP) technique to deposit the polymer and fullerene materials in separate deposition steps. The polymer layer is deposited first, using solvents and deposition conditions that optimize the polymer crystallinity for swelling and hole mobility. The fullerene layer is then deposited in a second step from a solvent that swells the polymer but does not dissolve it, allowing the fullerene to penetrate into the polymer underlayer to the desired degree. Careful comparison of composition- and thickness-matched BC and SqP devices shows that SqP not only produces more efficient devices but also leads to devices that behave more consistently.« less

Dental implant customization using numerical optimization design and 3-dimensional printing fabrication of zirconia ceramic.

PubMed

Cheng, Yung-Chang; Lin, Deng-Huei; Jiang, Cho-Pei; Lin, Yuan-Min

2017-05-01

This study proposes a new methodology for dental implant customization consisting of numerical geometric optimization and 3-dimensional printing fabrication of zirconia ceramic. In the numerical modeling, exogenous factors for implant shape include the thread pitch, thread depth, maximal diameter of implant neck, and body size. Endogenous factors are bone density, cortical bone thickness, and non-osseointegration. An integration procedure, including uniform design method, Kriging interpolation and genetic algorithm, is applied to optimize the geometry of dental implants. The threshold of minimal micromotion for optimization evaluation was 100 μm. The optimized model is imported to the 3-dimensional slurry printer to fabricate the zirconia green body (powder is bonded by polymer weakly) of the implant. The sintered implant is obtained using a 2-stage sintering process. Twelve models are constructed according to uniform design method and simulated the micromotion behavior using finite element modeling. The result of uniform design models yields a set of exogenous factors that can provide the minimal micromotion (30.61 μm), as a suitable model. Kriging interpolation and genetic algorithm modified the exogenous factor of the suitable model, resulting in 27.11 μm as an optimization model. Experimental results show that the 3-dimensional slurry printer successfully fabricated the green body of the optimization model, but the accuracy of sintered part still needs to be improved. In addition, the scanning electron microscopy morphology is a stabilized t-phase microstructure, and the average compressive strength of the sintered part is 632.1 MPa. Copyright © 2016 John Wiley & Sons, Ltd.

Polymer translocation under a pulling force: Scaling arguments and threshold forces

NASA Astrophysics Data System (ADS)

Menais, Timothée

2018-02-01

DNA translocation through nanopores is one of the most promising strategies for next-generation sequencing technologies. Most experimental and numerical works have focused on polymer translocation biased by electrophoresis, where a pulling force acts on the polymer within the nanopore. An alternative strategy, however, is emerging, which uses optical or magnetic tweezers. In this case, the pulling force is exerted directly at one end of the polymer, which strongly modifies the translocation process. In this paper, we report numerical simulations of both linear and structured (mimicking DNA) polymer models, simple enough to allow for a statistical treatment of the pore structure effects on the translocation time probability distributions. Based on extremely extended computer simulation data, we (i) propose scaling arguments for an extension of the predicted translocation times τ ˜N2F-1 over the moderate forces range and (ii) analyze the effect of pore size and polymer structuration on translocation times τ .

One-dimensional GIS-based model compared with a two-dimensional model in urban floods simulation.

PubMed

Lhomme, J; Bouvier, C; Mignot, E; Paquier, A

2006-01-01

A GIS-based one-dimensional flood simulation model is presented and applied to the centre of the city of Nîmes (Gard, France), for mapping flow depths or velocities in the streets network. The geometry of the one-dimensional elements is derived from the Digital Elevation Model (DEM). The flow is routed from one element to the next using the kinematic wave approximation. At the crossroads, the flows in the downstream branches are computed using a conceptual scheme. This scheme was previously designed to fit Y-shaped pipes junctions, and has been modified here to fit X-shaped crossroads. The results were compared with the results of a two-dimensional hydrodynamic model based on the full shallow water equations. The comparison shows that good agreements can be found in the steepest streets of the study zone, but differences may be important in the other streets. Some reasons that can explain the differences between the two models are given and some research possibilities are proposed.

Adsorption of flexible polymer chains on a surface: Effects of different solvent conditions

NASA Astrophysics Data System (ADS)

Martins, P. H. L.; Plascak, J. A.; Bachmann, M.

2018-05-01

Polymer chains undergoing a continuous adsorption-desorption transition are studied through extensive computer simulations. A three-dimensional self-avoiding walk lattice model of a polymer chain grafted onto a surface has been treated for different solvent conditions. We have used an advanced contact-density chain-growth algorithm, in which the density of contacts can be directly obtained. From this quantity, the order parameter and its fourth-order Binder cumulant are computed, as well as the corresponding critical exponents and the adsorption-desorption transition temperature. As the number of configurations with a given number of surface contacts and monomer-monomer contacts is independent of the temperature and solvent conditions, it can be easily applied to get results for different solvent parameter values without the need of any extra simulations. In analogy to continuous magnetic phase transitions, finite-size-scaling methods have been employed. Quite good results for the critical properties and phase diagram of very long single polymer chains have been obtained by properly taking into account the effects of corrections to scaling. The study covers all solvent effects, going from the limit of super-self-avoiding walks, characterized by effective monomer-monomer repulsion, to poor solvent conditions that enable the formation of compact polymer structures.

Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

PubMed

Ye, Long; Zhang, Shaoqing; Huo, Lijun; Zhang, Maojie; Hou, Jianhui

2014-05-20

As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account correlates the molecular structures of the 2D-conjugated BDT-based polymers with their photovoltaic properties. As a result, this Account can guide the molecular design of organic photovoltaic materials and the development of organic materials for other types of optoelectronic devices.

Interfacial growth as a model of tube-width heterogeneities in concentrated solutions of stiff polymers

NASA Astrophysics Data System (ADS)

Sharma, Rati; Cherayil, Binny J.

2013-06-01

Recent experimental measurements of the distribution P(w) of transverse chain fluctuations w in concentrated solutions of F-actin filaments [B. Wang, J Guan, S. M. Anthony, S. C. Bae, K. S. Schweizer, and S. Granick, Phys. Rev. Lett. 104, 118301 (2010), 10.1103/PhysRevLett.104.118301; J. Glaser, D. Chakraborty, K. Kroy, I. Lauter, M. Degawa, N. Kirchgessner, B. Hoffmann, R. Merkel, and M. Giesen, Phys. Rev. Lett. 105, 037801 (2010)], 10.1103/PhysRevLett.105.037801 are shown to be well-fit to an expression derived from a model of the conformations of a single harmonically confined weakly bendable rod. The calculation of P(w) is carried out essentially exactly within a path integral approach that was originally applied to the study of one-dimensional randomly growing interfaces. Our results are generally as successful in reproducing experimental trends as earlier approximate results obtained from more elaborate many-chain treatments of the confining tube potential.

On the membrane approximation in isothermal film casting

NASA Astrophysics Data System (ADS)

Hagen, Thomas

2014-08-01

In this work, a one-dimensional model for isothermal film casting is studied. Film casting is an important engineering process to manufacture thin films and sheets from a highly viscous polymer melt. The model equations account for variations in film width and film thickness, and arise from thinness and kinematic assumptions for the free liquid film. The first aspect of our study is a rigorous discussion of the existence and uniqueness of stationary solutions. This objective is approached via the argument principle, exploiting the homotopy invariance of a family of analytic functions. As our second objective, we analyze the linearization of the governing equations about stationary solutions. It is shown that solutions for the associated boundary-initial value problem are given by a strongly continuous semigroup of bounded linear operators. To reach this result, we cast the relevant Cauchy problem in a more accessible form. These transformed equations allow us insight into the regularity of the semigroup, thus yielding the validity of the spectral mapping theorem for the semigroup and the spectrally determined growth property.

Direct ink writing of 3D conductive polyaniline structures and rheological modelling

NASA Astrophysics Data System (ADS)

Holness, F. Benjamin; Price, Aaron D.

2018-01-01

The intractable nature of conjugated polymers (CP) leads to practical limitations in the fabrication of CP-based transducers having complex three-dimensional geometries. Conventional CP device fabrication processes have focused primarily on thin-film deposition techniques; this study explores novel additive manufacturing processes specifically developed for CP with the ultimate goal of increasing the functionality of CP sensors and actuators. Herein we employ automated polymer paste extrusion processes for the direct ink writing of 3D conductive polyaniline (PANI) structures. Realization of these structures was enabled through a modified fused filament fabrication delta robot equipped with an integrated polymer paste extruder to fabricate high-resolution 3D conductive PANI structures. The required processability of PANI was achieved by means of a counterion-induced thermal doping method. The effect of thermal doping on the PANI-DBSA paste by means of a constitutive relationship to describe the paste flow as a function of the thermal doping time is explored. This relationship is incorporated within a flow model to predict the extruded track width as a function of various process parameters including: print speed, gauge pressure, nozzle diameter, and pre-extrusion thermal doping time.

Fabrication of freestanding, microperforated membranes and their applications in microfluidics

PubMed Central

Zheng, Yizhe; Dai, Wen; Ryan, Declan; Wu, Hongkai

2010-01-01

This manuscript describes a convenient method for the fabrication of freestanding, microperforated membranes in photocurable polymers using only one step of photolithography. We used photosensitive prepolymers to make the membranes and photolithography to define the micropatterns. We demonstrated the fabrication of single- and multilayer microperforated membranes in SU-8 photoresist and Norland Optical Adhesive prepolymer. These membranes can be used to pattern surfaces in various materials and to fabricate complex three-dimensional microfluidic channel structures. PMID:21045933

Underwater striling engine design with modified one-dimensional model

NASA Astrophysics Data System (ADS)

Li, Daijin; Qin, Kan; Luo, Kai

2015-09-01

Stirling engines are regarded as an efficient and promising power system for underwater devices. Currently, many researches on one-dimensional model is used to evaluate thermodynamic performance of Stirling engine, but in which there are still some aspects which cannot be modeled with proper mathematical models such as mechanical loss or auxiliary power. In this paper, a four-cylinder double-acting Stirling engine for Unmanned Underwater Vehicles (UUVs) is discussed. And a one-dimensional model incorporated with empirical equations of mechanical loss and auxiliary power obtained from experiments is derived while referring to the Stirling engine computer model of National Aeronautics and Space Administration (NASA). The P-40 Stirling engine with sufficient testing results from NASA is utilized to validate the accuracy of this one-dimensional model. It shows that the maximum error of output power of theoretical analysis results is less than 18% over testing results, and the maximum error of input power is no more than 9%. Finally, a Stirling engine for UUVs is designed with Schmidt analysis method and the modified one-dimensional model, and the results indicate this designed engine is capable of showing desired output power.

The application of magnetic resonance microimaging to the visible light curing of dental resins. 3. Stray-field nuclear magnetic resonance imaging (STRAFI).

PubMed

Lloyd, C H; Scrimgeour, S N; Lane, D M; Hunter, G; McDonald, P J

2001-09-01

To investigate the application of stray-field nuclear magnetic resonance imaging (STRAFI) to the visible light curing of dental restorative materials. STRAFI can overcome peak broadening associated with the conventional magnetic resonance microimaging (MRM) of glassy polymers, and has the potential to image dental restorative resins at both low and high degrees of conversion. Cylindrical composite specimens were light-cured from one end to produce some that were fully cured throughout their length and others that were fully cured at one end and uncured at the other. A one-dimensional probe was used to measure the magnetisation in 40 microm thick slices at 100 microm intervals along the length of the specimen. A quadrature pulse sequence was applied and the magnetisation decay recorded in a train of eight echoes. A value for T(2) could be obtained only for the polymer (59+/-16 microms), therefore the echoes were summed to give an approximate indication of the degree of conversion. The echo sum for the monomer was significantly higher than that for the polymer. Differences in composite shade and cure time produced changes in the cure profiles. STRAFI produced measurements for both monomer and polymer in all stages of conversion that allowed cure profiles to be produced. Summing the decay echoes produced a qualitative measure of the condition of the material in the selected slice. The same data can be used to calculate T(2), a quantitative parameter. This first investigation has demonstrated that STRAFI is well suited to polymerisation studies.

Assembly of Nanorods into Designer Superstructures: The Role of Templating, Capillary Forces, Adhesion, and Polymer Hydration

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

Ciszek, Jacob W.; Huang, Ling; Tsonchev, Stefan

The assembly mechanism by which hundreds of thousands of two-segment gold-polypyrrole nanorods are assembled into kinetically controlled shape-directed superstructures is examined to predict the range of nanoparticle sizes and materials that can be utilized in their formation. Four processes are responsible for assembly: templating, capillary force assembly, adhesion, and polymer hydration. It is shown that templating, where rods are prepositioned for assembly, is scale invariant and that the energy-minimized state after this step is highly disordered. In addition, we predict that superstructures can be made independently from patterns of rods separated by a distance as small as six times themore » inter-rod spacing. Both modeling and experiment show that adhesion and polymer dehydration, which induces curvature in the superstructures, are applicable to other materials. However, the high surface energy and low elastic modulus of polypyrrole are advantageous toward generating three-dimensional structures, inducing curvature at gold/polypyrrole length ratios as large as 7:1.« less

Localized Enzymatic Degradation of Polymers: Physics and Scaling Laws

NASA Astrophysics Data System (ADS)

Lalitha Sridhar, Shankar; Vernerey, Franck

2018-03-01

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

Effect of ice-albedo feedback on global sensitivity in a one-dimensional radiative-convective climate model

NASA Technical Reports Server (NTRS)

Wang, W.-C.; Stone, P. H.

1980-01-01

The feedback between the ice albedo and temperature is included in a one-dimensional radiative-convective climate model. The effect of this feedback on global sensitivity to changes in solar constant is studied for the current climate conditions. This ice-albedo feedback amplifies global sensitivity by 26 and 39%, respectively, for assumptions of fixed cloud altitude and fixed cloud temperature. The global sensitivity is not affected significantly if the latitudinal variations of mean solar zenith angle and cloud cover are included in the global model. The differences in global sensitivity between one-dimensional radiative-convective models and energy balance models are examined. It is shown that the models are in close agreement when the same feedback mechanisms are included. The one-dimensional radiative-convective model with ice-albedo feedback included is used to compute the equilibrium ice line as a function of solar constant.

MAGIC with formaldehyde applied to dosimetry of HDR brachytherapy source

NASA Astrophysics Data System (ADS)

Marques; T; Fernandes; J; Barbi; G; Nicolucci; P; Baffa; O

2009-05-01

The use of polymer gel dosimeters in brachytherapy can allow the determination of three-dimensional dose distributions in large volumes and with high spatial resolution if an adequate calibration process is performed. One of the major issues in these experiments is the polymer gel response dependence on dose rate when high dose rate sources are used and the doses in the vicinity of the sources are to be determinated. In this study, the response of a modified MAGIC polymer gel with formaldehyde around an Iridium-192 HDR brachytherapy source is presented. Experimental results obtained with this polymer gel were compared with ionization chamber measurements and with Monte Carlo simulation with PENELOPE. A maximum difference of 3.10% was found between gel dose measurements and Monte Carlo simulation at a radial distance of 18 mm from the source. The results obtained show that the gel's response is strongly influenced by dose rate and that a different calibration should be used for the vicinity of the source and for regions of lower dose rates. The results obtained in this study show that, provided the proper calibration is performed, MAGIC with formaldehyde can be successfully used to accurate determinate dose distributions form high dose rate brachytherapy sources.

Shape forming by thermal expansion mismatch and shape memory locking in polymer/elastomer laminates

NASA Astrophysics Data System (ADS)

Yuan, Chao; Ding, Zhen; Wang, T. J.; Dunn, Martin L.; Qi, H. Jerry

2017-10-01

This paper studies a novel method to fabricate three-dimensional (3D) structure from 2D thermo-responsive shape memory polymer (SMP)/elastomer bilayer laminate. In this method, the shape change is actuated by the thermal mismatch strain between the SMP and the elastomer layers upon heating. However, the glass transition behavior of the SMP locks the material into a new 3D shape that is stable even upon cooling. Therefore, the second shape becomes a new permanent shape of the laminate. A theoretical model that accounts for the temperature-dependent thermomechanical behavior of the SMP material and thermal mismatch strain between the two layers is developed to better understand the underlying physics. Model predictions and experiments show good agreement and indicate that the theoretical model can well predict the bending behavior of the bilayer laminate. The model is then used in the optimal design of geometrical configuration and material selection. The latter also illustrates the requirement of thermomechanical behaviors of the SMP to lock the shape. Based on the fundamental understandings, several self-folding structures are demonstrated by the bilayer laminate design.

Formation of three-dimensional cell/polymer constructs for bone tissue engineering in a spinner flask and a rotating wall vessel bioreactor

NASA Technical Reports Server (NTRS)

Sikavitsas, Vassilios I.; Bancroft, Gregory N.; Mikos, Antonios G.; McIntire, L. V. (Principal Investigator)

2002-01-01

The aim of this study is to investigate the effect of the cell culture conditions of three-dimensional polymer scaffolds seeded with rat marrow stromal cells (MSCs) cultured in different bioreactors concerning the ability of these cells to proliferate, differentiate towards the osteoblastic lineage, and generate mineralized extracellular matrix. MSCs harvested from male Sprague-Dawley rats were culture expanded, seeded on three-dimensional porous 75:25 poly(D,L-lactic-co-glycolic acid) biodegradable scaffolds, and cultured for 21 days under static conditions or in two model bioreactors (a spinner flask and a rotating wall vessel) that enhance mixing of the media and provide better nutrient transport to the seeded cells. The spinner flask culture demonstrated a 60% enhanced proliferation at the end of the first week when compared to static culture. On day 14, all cell/polymer constructs exhibited their maximum alkaline phosphatase activity (AP). Cell/polymer constructs cultured in the spinner flask had 2.4 times higher AP activity than constructs cultured under static conditions on day 14. The total osteocalcin (OC) secretion in the spinner flask culture was 3.5 times higher than the static culture, with a peak OC secretion occurring on day 18. No considerable AP activity and OC secretion were detected in the rotating wall vessel culture throughout the 21-day culture period. The spinner flask culture had the highest calcium content at day 14. On day 21, the calcium deposition in the spinner flask culture was 6.6 times higher than the static cultured constructs and over 30 times higher than the rotating wall vessel culture. Histological sections showed concentration of cells and mineralization at the exterior of the foams at day 21. This phenomenon may arise from the potential existence of nutrient concentration gradients at the interior of the scaffolds. The better mixing provided in the spinner flask, external to the outer surface of the scaffolds, may explain the accelerated proliferation and differentiation of marrow stromal osteoblasts, and the localization of the enhanced mineralization on the external surface of the scaffolds. Copyright 2002 Wiley Periodicals, Inc.

Simulation of Water-Surface Elevations and Velocity Distributions at the U.S. Highway 13 Bridge over the Tar River at Greenville, North Carolina, Using One- and Two-Dimensional Steady-State Hydraulic Models

USGS Publications Warehouse

Wagner, Chad R.

2007-01-01

The use of one-dimensional hydraulic models currently is the standard method for estimating velocity fields through a bridge opening for scour computations and habitat assessment. Flood-flow contraction through bridge openings, however, is hydrodynamically two dimensional and often three dimensional. Although there is awareness of the utility of two-dimensional models to predict the complex hydraulic conditions at bridge structures, little guidance is available to indicate whether a one- or two-dimensional model will accurately estimate the hydraulic conditions at a bridge site. The U.S. Geological Survey, in cooperation with the North Carolina Department of Transportation, initiated a study in 2004 to compare one- and two-dimensional model results with field measurements at complex riverine and tidal bridges in North Carolina to evaluate the ability of each model to represent field conditions. The field data consisted of discharge and depth-averaged velocity profiles measured with an acoustic Doppler current profiler and surveyed water-surface profiles for two high-flow conditions. For the initial study site (U.S. Highway 13 over the Tar River at Greenville, North Carolina), the water-surface elevations and velocity distributions simulated by the one- and two-dimensional models showed appreciable disparity in the highly sinuous reach upstream from the U.S. Highway 13 bridge. Based on the available data from U.S. Geological Survey streamgaging stations and acoustic Doppler current profiler velocity data, the two-dimensional model more accurately simulated the water-surface elevations and the velocity distributions in the study reach, and contracted-flow magnitudes and direction through the bridge opening. To further compare the results of the one- and two-dimensional models, estimated hydraulic parameters (flow depths, velocities, attack angles, blocked flow width) for measured high-flow conditions were used to predict scour depths at the U.S. Highway 13 bridge by using established methods. Comparisons of pier-scour estimates from both models indicated that the scour estimates from the two-dimensional model were as much as twice the depth of the estimates from the one-dimensional model. These results can be attributed to higher approach velocities and the appreciable flow angles at the piers simulated by the two-dimensional model and verified in the field. Computed flood-frequency estimates of the 10-, 50-, 100-, and 500-year return-period floods on the Tar River at Greenville were also simulated with both the one- and two-dimensional models. The simulated water-surface profiles and velocity fields of the various return-period floods were used to compare the modeling approaches and provide information on what return-period discharges would result in road over-topping and(or) pressure flow. This information is essential in the design of new and replacement structures. The ability to accurately simulate water-surface elevations and velocity magnitudes and distributions at bridge crossings is essential in assuring that bridge plans balance public safety with the most cost-effective design. By compiling pertinent bridge-site characteristics and relating them to the results of several model-comparison studies, the framework for developing guidelines for selecting the most appropriate model for a given bridge site can be accomplished.

2-d and 1-d Nanomaterials Construction through Peptide Computational Design and Solution Assembly

NASA Astrophysics Data System (ADS)

Pochan, Darrin

Self-assembly of molecules is an attractive materials construction strategy due to its simplicity in application. By considering peptidic molecules in the bottom-up materials self-assembly design process, one can take advantage of inherently biomolecular attributes; intramolecular folding events, secondary structure, and electrostatic/H-bonding/hydrophobic interactions to define hierarchical material structure and consequent properties. Importantly, while biomimicry has been a successful strategy for the design of new peptide molecules for intermolecular assembly, computational tools have been developed to de novo design peptide molecules required for construction of pre-determined, desired nanostructures and materials. A new system comprised of coiled coil bundle motifs theoretically designed to assemble into designed, one and two-dimensional nanostructures will be introduced. The strategy provides the opportunity for arbitrary nanostructure formation, i.e. structures not observed in nature, with peptide molecules. Importantly, the desired nanostructure was chosen first while the peptides needed for coiled coil formation and subsequent nanomaterial formation were determined computationally. Different interbundle, two-dimensional nanostructures are stabilized by differences in amino acid composition exposed on the exterior of the coiled coil bundles. Computation was able to determine molecules required for different interbundle symmetries within two-dimensional sheets stabilized by subtle differences in amino acid composition of the inherent peptides. Finally, polymers were also created through covalent interactions between bundles that allowed formation of architectures spanning flexible network forming chains to ultra-stiff polymers, all with the same building block peptides. The success of the computational design strategy is manifested in the nanomaterial results as characterized by electron microscopy, scattering methods, and biophysical techniques. Support from NSF DMREF program under awards DMR-1234161 and DMR-1235084.

Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N‧-dimethylformamide

NASA Astrophysics Data System (ADS)

Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei; Zhang, Xia; Wang, Mei; Jin, Fan; Fan, Yu-hua

2017-04-01

Five functional coordination polymers (formic-based CPs) namely: {[Cu2(CHOO)3(bibp)2]·CHOO}n (1), {[Co2(CHOO)3(bibp)2]·NO3·H2O}n (2), {[Ni2(CHOO)3(bibp)2]·NO3·H2O}n (3) [Co(CHOO)2(bbibp)]n (4) and [Zn(CHOO)2(bbibp)]n (5) (bibp=4,4‧-bis(imidazolyl)biphenyl, bbibp=4,4‧-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N‧-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1-3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C-H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.

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

Steiner, J.L.; Lime, J.F.; Elson, J.S.

One dimensional TRAC transient calculations of the process inherent ultimate safety (PIUS) advanced reactor design were performed for a pump-trip SCRAM. The TRAC calculations showed that the reactor power response and shutdown were in qualitative agreement with the one-dimensional analyses presented in the PIUS Preliminary Safety Information Document (PSID) submitted by Asea Brown Boveri (ABB) to the US Nuclear Regulatory Commission for preapplication safety review. The PSID analyses were performed with the ABB-developed RIGEL code. The TRAC-calculated phenomena and trends were also similar to those calculated with another one-dimensional PIUS model, the Brookhaven National Laboratory developed PIPA code. A TRACmore » pump-trip SCRAM transient has also been calculated with a TRAC model containing a multi-dimensional representation of the PIUS intemal flow structures and core region. The results obtained using the TRAC fully one-dimensional PIUS model are compared to the RIGEL, PIPA, and TRAC multi-dimensional results.« less

Bioerodible System for Sequential Release of Multiple Drugs

PubMed Central

Sundararaj, Sharath C.; Thomas, Mark V.; Dziubla, Thomas D.; Puleo, David A.

2013-01-01

Because many complex physiological processes are controlled by multiple biomolecules, comprehensive treatment of certain disease conditions may be more effectively achieved by administration of more than one type of drug. Thus, the objective of the present research was to develop a multilayered, polymer-based system for sequential delivery of multiple drugs. The polymers used were cellulose acetate phthalate (CAP) complexed with Pluronic F-127 (P). After evaluating morphology of the resulting CAPP system, in vitro release of small molecule drugs and a model protein was studied from both single and multilayered devices. Drug release from single-layered CAPP films followed zero-order kinetics related to surface erosion of the association polymer. Release studies from multilayered CAPP devices showed the possibility of achieving intermittent release of one type of drug as well as sequential release of more than one type of drug. Mathematical modeling accurately predicted the release profiles for both single layer and multilayered devices. The present CAPP association polymer-based multilayer devices can be used for localized, sequential delivery of multiple drugs for the possible treatment of complex disease conditions, and perhaps for tissue engineering applications, that require delivery of more than one type of biomolecule. PMID:24096151

Conducting polymers with immobilised fibrillar collagen for enhanced neural interfacing.

PubMed

Liu, Xiao; Yue, Zhilian; Higgins, Michael J; Wallace, Gordon G

2011-10-01

Conducting polymers with pendant functionality are advantageous in various bionic and organic bioelectronic applications, as they allow facile incorporation of bio-regulative cues to provide bio-mimicry and conductive environments for cell growth, differentiation and function. In this work, polypyrrole substrates doped with chondroitin sulfate (CS), an extracellular matrix molecule bearing carboxylic acid moieties, were electrochemically synthesized and conjugated with type I collagen. During the coupling process, the conjugated collagen formed a 3-dimensional fibrillar matrix in situ at the conducting polymer interface, as evidenced by atomic force microscopy (AFM) and fluorescence microscopy under aqueous physiological conditions. Cyclic voltammetry (CV) and impedance measurement confirmed no significant reduction in the electroactivity of the fibrillar collagen-modified conducting polymer substrates. Rat pheochromocytoma (nerve) cells showed increased differentiation and neurite outgrowth on the fibrillar collagen, which was further enhanced through electrical stimulation of the underlying conducting polymer substrate. Our study demonstrates that the direct coupling of ECM components such as collagen, followed by their further self-assembly into 3-dimensional matrices, has the potential to improve the neural-electrode interface of implant electrodes by encouraging nerve cell attachment and differentiation. Copyright © 2011 Elsevier Ltd. All rights reserved.

All-Polymer Solar Cell Performance Optimized via Systematic Molecular Weight Tuning of Both Donor and Acceptor Polymers

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

Zhou, Nanjia; Dudnik, Alexander S.; Li, Ting I. N. G.

2016-01-21

The influence of the number-average molecular weight (Mn) on the blend film morphology and photovoltaic performance of all-polymer solar cells (APSCs) fabricated with the donor polymer poly[5-(2-hexyldodecyl)-1,3-thieno[3,4-c]pyrrole-4,6-dione-alt-5,5-(2,5-bis(3-dodecylthiophen-2-yl)thiophene)] (PTPD3T) and acceptor polymer poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2); N2200) is systematically investigated. The Mn effect analysis of both PTPD3T and N2200 is enabled by implementing a polymerization strategy which produces conjugated polymers with tunable Mns. Experimental and coarse-grain modeling results reveal that systematic Mn variation greatly influences both intrachain and interchain interactions and ultimately the degree of phase separation and morphology evolution. Specifically, increasing Mn for both polymers shrinks blend film domain sizes and enhancesmore » donor–acceptor polymer–polymer interfacial areas, affording increased short-circuit current densities (Jsc). However, the greater disorder and intermixed feature proliferation accompanying increasing Mn promotes charge carrier recombination, reducing cell fill factors (FF). The optimized photoactive layers exhibit well-balanced exciton dissociation and charge transport characteristics, ultimately providing solar cells with a 2-fold PCE enhancement versus devices with nonoptimal Mns. Overall, it is shown that proper and precise tuning of both donor and acceptor polymer Mns is critical for optimizing APSC performance. In contrast to reports where maximum power conversion efficiencies (PCEs) are achieved for the highest Mns, the present two-dimensional Mn optimization matrix strategy locates a PCE “sweet spot” at intermediate Mns of both donor and acceptor polymers. This study provides synthetic methodologies to predictably access conjugated polymers with desired Mn and highlights the importance of optimizing Mn for both polymer components to realize the full potential of APSC performance.« less

Diffusion in inhomogeneous polymer membranes

NASA Astrophysics Data System (ADS)

Kasargod, Sameer S.; Adib, Farhad; Neogi, P.

1995-10-01

The dual mode sorption solubility isotherms assume, and in instances Zimm-Lundberg analysis of the solubilities show, that glassy polymers are heterogeneous and that the distribution of the solute in the polymer is also inhomogeneous. Under some conditions, the heterogeneities cannot be represented as holes. A mathematical model describing diffusion in inhomogeneous polymer membranes is presented using Cahn and Hilliard's gradient theory. The fractional mass uptake is found to be proportional to the fourth root of time rather than the square root, predicted by Fickian diffusion. This type of diffusion is classified as pseudo-Fickian. The model is compared with one experimental result available. A negative value of the persistence factor is obtained and the results are interpreted.

Switchable polarization in an unzipped graphene oxide monolayer.

PubMed

Noor-A-Alam, Mohammad; Shin, Young-Han

2016-08-14

Ferroelectricity in low-dimensional oxide materials is generally suppressed at the scale of a few nanometers, and has attracted considerable attention from both fundamental and technological aspects. Graphene is one of the thinnest materials (one atom thick). Therefore, engineering switchable polarization in non-polar pristine graphene could potentially lead to two-dimensional (2D) ferroelectric materials. In the present study, based on density functional theory, we show that an unzipped graphene oxide (UGO) monolayer can exhibit switchable polarization due to its foldable bonds between the oxygen atom and two carbon atoms underneath the oxygen. We find that a free standing UGO monolayer exhibits antiferroelectric switchable polarization. A UGO monolayer can be obtained as an intermediate product during the chemical exfoliation process of graphene. Interestingly, despite its dimensionality, our estimated polarization in a UGO monolayer is comparable to that in bulk ferroelectric materials (e.g., ferroelectric polymers). Our calculations could help realize antiferroelectric switchable polarization in 2D materials, which could find various potential applications in nanoscale devices such as sensors, actuators, and capacitors with high energy-storage density.

Direct simulation of polymer drag reduction in free shear flows and vortex dipoles

NASA Technical Reports Server (NTRS)

Orlandi, P.; Homsy, G. M.; Azaiez, J.

1992-01-01

One of the most efficient techniques for drag reduction is the injection of polymers near a wall which can achieve a reduction in drag up to 80 percent. Several experimental observations tend to indicate that polymers modify the turbulence structures within the buffer layer and show that the changes consist of a weakening of the strength of the streamwise vortices. In this paper, we investigate the effects of viscoelasticity on two different types of flows: the vortex dipole impinging walls to model streamwise vortices in a turbulent boundary layer and the mixing layer that represents free shear flows. For this purpose, we examined three different rheological models: the Oldroyd-B model, the Jeffrey's corotational model, and the FENE-P model.

Polarization manipulation in single refractive prism based holography lithography

NASA Astrophysics Data System (ADS)

Xiong, Wenjie; Xu, Yi; Xiao, Yujian; Lv, Xiaoxu; Wu, Lijun

2015-01-01

We propose theoretically and demonstrate experimentally a simple but effective strategy for polarization manipulation in single refractive prism based holographic lithography. By tuning the polarization of a single laser beam, we can obtain the pill shape interference pattern with a high-contrast where a complex optical setup and multiple polarizers are needed in the conventional holography lithography. Fabrication of pill shape two-dimensional polymer photonic crystals using one beam and one shoot holography lithography is shown as an example to support our theoretical results. This integrated polarization manipulation technique can release the crucial stability restrictions imposed on the multiple beams holography lithography.

One-dimensional magnetic nanocomposites with attapulgites as templates: Growth, formation mechanism and magnetic alignment

NASA Astrophysics Data System (ADS)

Fu, Meng; Li, Xiangming; Jiang, Rui; Zhang, Zepeng

2018-05-01

Magnetic nanocomposite composed of attapulgite and Fe3O4 was synthesized by a simple and facile co-precipitation method. Its structure and morphology was verified using X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. Although the difficulty of forming uniform Fe3O4 on the attapulgite surface was discussed in detail in this study, one-dimensional magnetic nanorod with attapulgites as core and Fe3O4 as uniform shell was implemented for the first time using a cationic polymer surfactant, polyethylenimine. Polyethylenimine concentration, Fe3+/Fe2+ concentration and temperature were controlled to investigate the morphological evolutions of this nanocomposite. It was found that a uniform shell could be available with thickness tuning from 10 nm to 40 nm when Fe3+ concentration ranged from 0.01 mol/L to 0.03 mol/L meanwhile the polyethylenimine concentration was kept at 0.2 mg/mL and the temperature was kept at 60-80 °C. Finally, a possible mechanism for the formation of the Fe3O4 shell was suggested. The polyethylenimine on the surface of the attapulgites first adsorbed Fe3+/Fe2+ and then released under the action of alkali. It acted as a linker for the Fe3O4 nanoparticles nucleation in situ. The synthesized one-dimensional nanocomposites exhibit the superparamagnetism and fast response to an external magnetic field. The alignment of attapulgite-Fe3O4 one-dimensional nanocomposite along the external magnetic field was demonstrated. It provides promising candidates for building blocks and functional devices, which are low cost, non-toxic and eco-friendly, and opens the door for the application of attapulgite as one-dimensional nanomaterials.

A 3D Polymer Based Printed Two-Dimensional Laser Scanner

NASA Astrophysics Data System (ADS)

Oyman, H. A.; Gokdel, Y. D.; Ferhanoglu, O.; Yalcinkaya, A. D.

2016-10-01

A two-dimensional (2D) polymer based scanning mirror with magnetic actuation is developed for imaging applications. Proposed device consists of a circular suspension holding a rectangular mirror and can generate a 2D scan pattern. Three dimensional (3D) printing technology which is used for implementation of the device, offers added flexibility in controlling the cross-sectional profile as well as the stress distribution compared to the traditional planar process technologies. The mirror device is developed to meet a portable, miniaturized confocal microscope application in mind, delivering 4.5 and 4.8 degrees of optical scan angles at 111 and 267 Hz, respectively. As a result of this mechanical performance, the resulting microscope incorporating the mirror is estimated to accomplish a field of view (FOV) of 350 µm × 350 µm.

Technology and Development of Self-Reinforced Polymer Composites

NASA Astrophysics Data System (ADS)

Alcock, Ben; Peijs, Ton

In recent years there has been an increasing amount of interest, both commercially and scientifically, in the emerging field of "self-reinforced polymer composites". These materials, which are sometimes also referred to as "single polymer composites", or "all-polymer composites", were first conceived in the 1970s, and are now beginning to appear in a range of commercial products. While high mechanical performance polymer fibres or tapes are an obvious precursor for composite development, various different technologies have been developed to consolidate these into two- or three-dimensional structures. This paper presents a review of the various processing techniques that have been reported in the literature for the manufacture of self-reinforced polymer composites from fibres or tapes of different polymers, and so exploit the fibre or tape performance in a commercial material or product.

Entanglement Area Law in Disordered Free Fermion Anderson Model in One, Two, and Three Dimensions

DOE PAGES

Pouranvari, Mohammad; Zhang, Yuhui; Yang, Kun

2015-01-01

We calculate numerically the entanglement entropy of free fermion ground states in one-, two-, and three-dimensional Anderson models and find that it obeys the area law as long as the linear size of the subsystem is sufficiently larger than the mean free path. This result holds in the metallic phase of the three-dimensional Anderson model, where the mean free path is finite although the localization length is infinite. Relation between the present results and earlier ones on area law violation in special one-dimensional models that support metallic phases is discussed.

Entanglement Area Law in Disordered Free Fermion Anderson Model in One, Two, and Three Dimensions

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

Pouranvari, Mohammad; Zhang, Yuhui; Yang, Kun

We calculate numerically the entanglement entropy of free fermion ground states in one-, two-, and three-dimensional Anderson models and find that it obeys the area law as long as the linear size of the subsystem is sufficiently larger than the mean free path. This result holds in the metallic phase of the three-dimensional Anderson model, where the mean free path is finite although the localization length is infinite. Relation between the present results and earlier ones on area law violation in special one-dimensional models that support metallic phases is discussed.

Fourier decomposition of polymer orientation in large-amplitude oscillatory shear flow

DOE PAGES

Giacomin, A. J.; Gilbert, P. H.; Schmalzer, A. M.

2015-03-19

In our previous work, we explored the dynamics of a dilute suspension of rigid dumbbells as a model for polymeric liquids in large-amplitude oscillatory shear flow, a flow experiment that has gained a significant following in recent years. We chose rigid dumbbells since these are the simplest molecular model to give higher harmonics in the components of the stress response. We derived the expression for the dumbbell orientation distribution, and then we used this function to calculate the shear stress response, and normal stress difference responses in large-amplitude oscillatory shear flow. In this paper, we deepen our understanding of themore » polymer motion underlying large-amplitude oscillatory shear flow by decomposing the orientation distribution function into its first five Fourier components (the zeroth, first, second, third, and fourth harmonics). We use three-dimensional images to explore each harmonic of the polymer motion. Our analysis includes the three most important cases: (i) nonlinear steady shear flow (where the Deborah number λω is zero and the Weissenberg number λγ 0 is above unity), (ii) nonlinear viscoelasticity (where both λω and λγ 0 exceed unity), and (iii) linear viscoelasticity (where λω exceeds unity and where λγ 0 approaches zero). We learn that the polymer orientation distribution is spherical in the linear viscoelastic regime, and otherwise tilted and peanut-shaped. We find that the peanut-shaping is mainly caused by the zeroth harmonic, and the tilting, by the second. The first, third, and fourth harmonics of the orientation distribution make only slight contributions to the overall polymer motion.« less

An elasto-viscoplastic interface model for investigating the constitutive behavior of nacre

NASA Astrophysics Data System (ADS)

Tang, H.; Barthelat, F.; Espinosa, H. D.

2007-07-01

In order to better understand the strengthening mechanism observed in nacre, we have developed an interface computational model to simulate the behavior of the organic present at the interface between aragonite tablets. In the model, the single polymer-chain behavior is characterized by the worm-like-chain (WLC) model, which is in turn incorporated into the eight-chain cell model developed by Arruda and Boyce [Arruda, E.M., Boyce, M.C., 1993a. A three-dimensional constitutive model for the large stretches, with application to polymeric glasses. Int. J. Solids Struct. 40, 389-412] to achieve a continuum interface constitutive description. The interface model is formulated within a finite-deformation framework. A fully implicit time-integration algorithm is used for solving the discretized governing equations. Finite element simulations were performed on a representative volume element (RVE) to investigate the tensile response of nacre. The staggered arrangement of tablets and interface waviness obtained experimentally by Barthelat et al. [Barthelat, F., Tang, H., Zavattieri, P.D., Li, C.-M., Espinosa, H.D., 2007. On the mechanics of mother-of-pearl: a key feature in the material hierarchical structure. J. Mech. Phys. Solids 55 (2), 306-337] was included in the RVE simulations. The simulations showed that both the rate-dependence of the tensile response and hysteresis loops during loading, unloading and reloading cycles were captured by the model. Through a parametric study, the effect of the polymer constitutive response during tablet-climbing and its relation to interface hardening was investigated. It is shown that stiffening of the organic material is not required to achieve the experimentally observed strain hardening of nacre during tension. In fact, when ratios of contour length/persistent length experimentally identified are employed in the simulations, the predicted stress-strain behavior exhibits a deformation hardening consistent with the one measured experimentally and also captured by the phenomenological cohesive model used in the study carried out by Barthelat et al. [Barthelat, F., Tang, H., Zavattieri, P.D., Li, C.-M., Espinosa, H.D., 2007. On the mechanics of mother-of-pearl: a key feature in the material hierarchical structure. J. Mech. Phys. Solids 55 (2), 306-337]. The simulation results also reveal that the bulk modulus of the polymer controls the rate of hardening, feature not captured by more simple cohesive laws.

Ab initio quantum mechanical calculation of the reaction probability for the Cl-+PH2Cl→ClPH2+Cl- reaction

NASA Astrophysics Data System (ADS)

Farahani, Pooria; Lundberg, Marcus; Karlsson, Hans O.

2013-11-01

The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2Cl→ClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

Effects of build parameters on linear wear loss in plastic part produced by fused deposition modeling

NASA Astrophysics Data System (ADS)

Mohamed, Omar Ahmed; Masood, Syed Hasan; Bhowmik, Jahar Lal

2017-07-01

Fused Deposition Modeling (FDM) is one of the prominent additive manufacturing technologies for producing polymer products. FDM is a complex additive manufacturing process that can be influenced by many process conditions. The industrial demands required from the FDM process are increasing with higher level product functionality and properties. The functionality and performance of FDM manufactured parts are greatly influenced by the combination of many various FDM process parameters. Designers and researchers always pay attention to study the effects of FDM process parameters on different product functionalities and properties such as mechanical strength, surface quality, dimensional accuracy, build time and material consumption. However, very limited studies have been carried out to investigate and optimize the effect of FDM build parameters on wear performance. This study focuses on the effect of different build parameters on micro-structural and wear performance of FDM specimens using definitive screening design based quadratic model. This would reduce the cost and effort of additive manufacturing engineer to have a systematic approachto make decision among the manufacturing parameters to achieve the desired product quality.

Super-resolution optical microscopy resolves network morphology of smart colloidal microgels.

PubMed

Bergmann, Stephan; Wrede, Oliver; Huser, Thomas; Hellweg, Thomas

2018-02-14

We present a new method to resolve the network morphology of colloidal particles in an aqueous environment via super-resolution microscopy. By localization of freely diffusing fluorophores inside the particle network we can resolve the three dimensional structure of one species of colloidal particles (thermoresponsive microgels) without altering their chemical composition through copolymerization with fluorescent monomers. Our approach utilizes the interaction of the fluorescent dye rhodamine 6G with the polymer network to achieve an indirect labeling. We calculate the 3D structure from the 2D images and compare the structure to previously published models for the microgel morphology, e.g. the fuzzy sphere model. To describe the differences in the data an extension of this model is suggested. Our method enables the tailor-made fabrication of colloidal particles which are used in various applications, such as paints or cosmetics, and are promising candidates for drug delivery, smart surface coatings, and nanocatalysis. With the precise knowledge of the particle morphology an understanding of the underlying structure-property relationships for various colloidal systems is possible.

Electrochemical kinetic and mass transfer model for direct ethanol alkaline fuel cell (DEAFC)

NASA Astrophysics Data System (ADS)

Abdullah, S.; Kamarudin, S. K.; Hasran, U. A.; Masdar, M. S.; Daud, W. R. W.

2016-07-01

A mathematical model is developed for a liquid-feed DEAFC incorporating an alkaline anion-exchange membrane. The one-dimensional mass transport of chemical species is modelled using isothermal, single-phase and steady-state assumptions. The anode and cathode electrochemical reactions use the Tafel kinetics approach, with two limiting cases, for the reaction order. The model fully accounts for the mixed potential effects of ethanol oxidation at the cathode due to ethanol crossover via an alkaline anion-exchange membrane. In contrast to a polymer electrolyte membrane model, the current model considers the flux of ethanol at the membrane as the difference between diffusive and electroosmotic effects. The model is used to investigate the effects of the ethanol and alkali inlet feed concentrations at the anode. The model predicts that the cell performance is almost identical for different ethanol concentrations at a low current density. Moreover, the model results show that feeding the DEAFC with 5 M NaOH and 3 M ethanol at specific operating conditions yields a better performance at a higher current density. Furthermore, the model indicates that crossover effects on the DEAFC performance are significant. The cell performance decrease from its theoretical value when a parasitic current is enabled in the model.

Three-dimensional bioprinting of cell-laden constructs with polycaprolactone protective layers for using various thermoplastic polymers.

PubMed

Kim, Byoung Soo; Jang, Jinah; Chae, Suhun; Gao, Ge; Kong, Jeong-Sik; Ahn, Minjun; Cho, Dong-Woo

2016-08-22

Three-dimensional (3D) cell-printed constructs have been recognized as promising biological substitutes for tissue/organ regeneration. They provide tailored physical properties and biological cues via multi-material printing process. In particular, hybrid bioprinting, enabling to use biodegradable synthetic polymers as framework, has been an attractive method to support weak hydrogels. The constructs with controlled architecture and high shape fidelity were fabricated through this method, depositing spatial arrangement of multi-cell types into microscale constructs. Among biodegradable synthetic polymers, polycaprolactone (PCL) has been commonly chosen in fabrication of cell-printed constructs because of its low melting temperature of 60 °C to be dispensed with extrusion-based bioprinting system. However, in addition to PCL, various synthetic polymers have been widely applied for tissue regeneration. These polymers have distinctive characteristics essential for tissue/organ regeneration. Nevertheless, it is difficult to use some polymers, such as poly (lactic-co-glycolic acid) (PLGA) and polylactic acid (PLA) with 3D bioprinting technology because of their high melting temperature to be dispensed, which can result in thermal damage to the cells in the printed constructs during the fabrication process. We present a novel bioprinting method to use various synthetic polymers in fabrication of cell-printed constructs. PCL was introduced as a protective layer to prevent thermal damage caused by high temperature of polymers during fabrication. Remarkable improvement in cellular activities in the printed constructs with PCL layers was observed compared with the construct without PCL. This bioprinting method can be applied to fabricate more tissue-like constructs through the use of various biomaterials.

A viscoelastic model for dielectric elastomers based on a continuum mechanical formulation and its finite element implementation

NASA Astrophysics Data System (ADS)

Bueschel, A.; Klinkel, S.; Wagner, W.

2011-04-01

Smart materials are active and multifunctional materials, which play an important part for sensor and actuator applications. These materials have the potential to transform passive structures into adaptive systems. However, a prerequisite for the design and the optimization of these materials is, that reliable models exist, which incorporate the interaction between the different combinations of thermal, electrical, magnetic, optical and mechanical effects. Polymeric electroelastic materials, so-called electroactive polymer (EAP), own the characteristic to deform if an electric field is applied. EAP's possesses the benefit that they share the characteristic of polymers, these are lightweight, inexpensive, fracture tolerant, elastic, and the chemical and physical structure is well understood. However, the description "electroactive polymer" is a generic term for many kinds of different microscopic mechanisms and polymeric materials. Based on the laws of electromagnetism and elasticity, a visco-electroelastic model is developed and implemented into the finite element method (FEM). The presented three-dimensional solid element has eight nodes and trilinear interpolation functions for the displacement and the electric potential. The continuum mechanics model contains finite deformations, the time dependency and the nearly incompressible behavior of the material. To describe the possible, large time dependent deformations, a finite viscoelastic model with a split of the deformation gradient is used. Thereby the time dependent characteristic of polymeric materials is incorporated through the free energy function. The electromechanical interactions are considered by the electrostatic forces and inside the energy function.

Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

NASA Astrophysics Data System (ADS)

Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

2015-04-01

The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [{Mn(acacen)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]2 (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]3[Re(CN)7]2 complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

Computational conformational antimicrobial analysis developing mechanomolecular theory for polymer biomaterials in materials science and engineering

NASA Astrophysics Data System (ADS)

Petersen, Richard C.

2014-03-01

Single-bond rotations or pyramidal inversions tend to either hide or expose relative energies that exist for atoms with nonbonding lone-pair electrons. Availability of lone-pair electrons depends on overall molecular electron distributions and differences in the immediate polarity of the surrounding pico/nanoenvironment. Stereochemistry three-dimensional aspects of molecules provide insight into conformations through single-bond rotations with associated lone-pair electrons on oxygen atoms in addition to pyramidal inversions with nitrogen atoms. When electrons are protected, potential energy is sheltered toward an energy minimum value to compatibilize molecularly with nonpolar environments. When electrons are exposed, maximum energy is available toward polar environment interactions. Computational conformational analysis software calculated energy profiles that exist during specific oxygen ether single-bond rotations with easy-to-visualize three-dimensional models for the trichlorinated bisaromatic ether triclosan antimicrobial polymer additive. As shown, fluctuating alternating bond rotations can produce complex interactions between molecules to provide entanglement strength for polymer toughness or alternatively disrupt weak secondary bonds of attraction to lower resin viscosity for new additive properties with nonpolar triclosan as a hydrophobic toughening/wetting agent. Further, bond rotations involving lone-pair electrons by a molecule at a nonpolar-hydrocarbon-membrane/polar-biologic-fluid interface might become sufficiently unstable to provide free mechanomolecular energies to disrupt weaker microbial membranes, for membrane transport of molecules into cells, provide cell signaling/recognition/defense and also generate enzyme mixing to speed reactions.

Verification of the modified model of the drying process of a polymer liquid film on a flat substrate by experiment (2): through more accurate experiment

NASA Astrophysics Data System (ADS)

Kagami, Hiroyuki

2006-05-01

We have proposed and modified a model of drying process of polymer solution coated on a flat substrate for flat polymer film fabrication and have presented the fruits through Photomask Japan 2002, 2003, 2004 and so on. And for example numerical simulation of the model qualitatively reappears a typical thickness profile of the polymer film formed after drying, that is, the profile that the edge of the film is thicker and just the region next to the edge's bump is thinner. Then we have clarified dependence of distribution of polymer molecules on a flat substrate on a various parameters based on analysis of many numerical simulations. Then we done a few kinds of experiments so as to verify the modified model and reported the initial result of them through Photomask Japan 2005. Through the initial result we could observe some results supporting the modified model. But we could not observe a characteristic region of a valley next to the edge's bump of a polymer film after drying because a shape of a solution's film coated on a substrate in the experiment was different from one in resists' coating and drying process or imagined in the modified model. In this study, we improved above difference between experiment and the model and did experiments for verification again with a shape of a solution's film coated on a substrate coincident with one imagined in the modified model and using molar concentration. As a result, some were verified more strongly and some need to be examined again. That is, we could confirm like results of last experiment that the smaller average molecular weight of Metoloses was, the larger the gradient of thickness profile of a polymer thin film was. But we could not observe a depression just inside the edge of the thin film also in this improved experiment. We may be able to enumerate the fact that not an organic solution but an aqueous solution was used in the experiment as the cause of non-formation of the depression.

Power-law creep behavior of a semiflexible chain.

PubMed

Majumdar, Arnab; Suki, Béla; Rosenblatt, Noah; Alencar, Adriano M; Stamenović, Dimitrije

2008-10-01

Rheological properties of adherent cells are essential for their physiological functions, and microrheological measurements on living cells have shown that their viscoelastic responses follow a weak power law over a wide range of time scales. This power law is also influenced by mechanical prestress borne by the cytoskeleton, suggesting that cytoskeletal prestress determines the cell's viscoelasticity, but the biophysical origins of this behavior are largely unknown. We have recently developed a stochastic two-dimensional model of an elastically joined chain that links the power-law rheology to the prestress. Here we use a similar approach to study the creep response of a prestressed three-dimensional elastically jointed chain as a viscoelastic model of semiflexible polymers that comprise the prestressed cytoskeletal lattice. Using a Monte Carlo based algorithm, we show that numerical simulations of the chain's creep behavior closely correspond to the behavior observed experimentally in living cells. The power-law creep behavior results from a finite-speed propagation of free energy from the chain's end points toward the center of the chain in response to an externally applied stretching force. The property that links the power law to the prestress is the chain's stiffening with increasing prestress, which originates from entropic and enthalpic contributions. These results indicate that the essential features of cellular rheology can be explained by the viscoelastic behaviors of individual semiflexible polymers of the cytoskeleton.

Nanoparticle mediated micromotor motion.

PubMed

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

2015-03-21

In this paper, we report the utilization of nanoparticles to mediate the motion of a polymer single crystal catalytic micromotor. Micromotors have been fabricated by directly self-assembling functional nanoparticles (platinum and iron oxide nanoparticles) onto one or both sides of two-dimensional polymer single crystals. We show that the moving velocity of these micromotors in fluids can be readily tuned by controlling the nanoparticles' surface wettability and catalytic activity. A 3 times velocity increase has been achieved for a hydrophobic micromotor as opposed to the hydrophilic ones. Furthermore, we demonstrate that the catalytic activity of platinum nanoparticles inside the micromotor can be enhanced by their synergetic interactions with iron oxide nanoparticles and an electric field. Both strategies lead to dramatically increased moving velocities, with the highest value reaching ∼200 μm s(-1). By decreasing the nanoparticles' surface wettability and increasing their catalytic activity, a maximum of a ∼10-fold increase in the moving speed of the nanoparticle based micromotor can be achieved. Our results demonstrate the advantages of using nanoparticles in micromotor systems.

Directional change in tunneling of subterranean termites (Isoptera: Rhinotermitidae) in response to decayed wood attractants.

PubMed

Su, Nan-Yao

2005-04-01

Wood discs decayed with brown rot fungi and polymer discs impregnated with acetone extract of decayed wood were embedded in sand of a two-dimensional foraging arena to evaluate their attractant potential in directing termite tunnels toward them. Termites were released near one arena corner and were guided to follow the physical guideline of the arena edges. In the absence of the attractants, termites generally formed a relatively linear tunnel along the edges. When decayed wood discs or treated polymer discs were placed in wet sand near one side of the arena, termite tunnels departed from the arena edges and were oriented toward them. The attraction distance ranged from 12 to 18 cm. The attractant properties were most likely water soluble and permeated through wet sand to cause termites to change their orientation. The results demonstrated that when such attractants are placed near a bait station in the field, they may be used to direct termite foraging toward the station.

catena-Poly[[[triaqua­sulfatozinc(II)]-μ-3,3′-bis­(3-pyrid­yl)-1,1′-(m-phenyl­ene)diurea] methanol solvate monohydrate

PubMed Central

Adarsh, N. N.; Dastidar, Parthasarathi

2010-01-01

In the title coordination polymer, {[Zn(SO4)(C18H16N6O2)(H2O)3]·CH3OH·H2O}n, the Zn2+ ion adopts a slightly distorted cis-ZnN2O4 octa­hedral geometry arising from three coordinated water mol­ecules, one sulfate ion and two bridging 3,3′-bis­(3-pyrid­yl)-1,1′-(m-phenyl­ene)diurea (bpmpbu) ligands. The dihedral angles between the central benzene ring and two terminal pyridine rings of the bpmbpu mol­ecule are 10.58 (17) and 34.63 (16)°. In the crystal, the ligands bridge the ZnII ions, thus generating a one-dimensional zigzag coordination polymer propagating in [010]. The crystal structure features extensive N—H⋯O and O—H⋯O hydrogen-bonding inter­actions. PMID:21580512

Universal Sequence Replication, Reversible Polymerization and Early Functional Biopolymers: A Model for the Initiation of Prebiotic Sequence Evolution

PubMed Central

Walker, Sara Imari; Grover, Martha A.; Hud, Nicholas V.

2012-01-01

Many models for the origin of life have focused on understanding how evolution can drive the refinement of a preexisting enzyme, such as the evolution of efficient replicase activity. Here we present a model for what was, arguably, an even earlier stage of chemical evolution, when polymer sequence diversity was generated and sustained before, and during, the onset of functional selection. The model includes regular environmental cycles (e.g. hydration-dehydration cycles) that drive polymers between times of replication and functional activity, which coincide with times of different monomer and polymer diffusivity. Template-directed replication of informational polymers, which takes place during the dehydration stage of each cycle, is considered to be sequence-independent. New sequences are generated by spontaneous polymer formation, and all sequences compete for a finite monomer resource that is recycled via reversible polymerization. Kinetic Monte Carlo simulations demonstrate that this proposed prebiotic scenario provides a robust mechanism for the exploration of sequence space. Introduction of a polymer sequence with monomer synthetase activity illustrates that functional sequences can become established in a preexisting pool of otherwise non-functional sequences. Functional selection does not dominate system dynamics and sequence diversity remains high, permitting the emergence and spread of more than one functional sequence. It is also observed that polymers spontaneously form clusters in simulations where polymers diffuse more slowly than monomers, a feature that is reminiscent of a previous proposal that the earliest stages of life could have been defined by the collective evolution of a system-wide cooperation of polymer aggregates. Overall, the results presented demonstrate the merits of considering plausible prebiotic polymer chemistries and environments that would have allowed for the rapid turnover of monomer resources and for regularly varying monomer/polymer diffusivities. PMID:22493682

Numerical Investigation of Delamination in Drilling of Carbon Fiber Reinforced Polymer Composites

NASA Astrophysics Data System (ADS)

Tang, Wenliang; Chen, Yan; Yang, Haojun; Wang, Hua; Yao, Qiwei

2018-03-01

Drilling of carbon fiber reinforced polymer (CFRP) is a challenging task in modern manufacturing sector and machining induced delamination is one of the major problems affecting assembly precision. In this work, a new three-dimensional (3D) finite element model is developed to study the chip formation and entrance delamination in drilling of CFRP composites on the microscopic level. Fiber phase, matrix phase and equivalent homogeneous phase in the multi-phase model have different constitutive behaviors, respectively. A comparative drilling test, in which the cement carbide drill and unidirectional CFRP laminate are employed, is conducted to validate the proposedmodel in terms of the delamination and the similar changing trend is obtained. Microscopic mechanism of entrance delamination together with the chip formation process at four special fiber cutting angles (0°, 45°, 90° and 135°) is investigated. Moreover, the peeling force is also predicted. The results show that the delamination occurrence and the chip formation are both strongly dependent on the fiber cutting angle. The length of entrance delamination rises with increasing fiber cutting angles. Negligible delamination at 0° is attributed to the compression by the minor flank face. For 45° and 90°, the delamination resulted from the mode III fracture. At 135°, serious delamination which is driven by the mode I and III fractures is more inclined to occur and the peeling force reaches its maximum. Such numerical models can help understand the mechanism of hole entrance delamination further and provide guidance for the damage-free drilling of CFRP.

FIB and MIP: understanding nanoscale porosity in molecularly imprinted polymers via 3D FIB/SEM tomography.

PubMed

Neusser, G; Eppler, S; Bowen, J; Allender, C J; Walther, P; Mizaikoff, B; Kranz, C

2017-10-05

We present combined focused ion beam/scanning electron beam (FIB/SEM) tomography as innovative method for differentiating and visualizing the distribution and connectivity of pores within molecularly imprinted polymers (MIPs) and non-imprinted control polymers (NIPs). FIB/SEM tomography is used in cell biology for elucidating three-dimensional structures such as organelles, but has not yet been extensively applied for visualizing the heterogeneity of nanoscopic pore networks, interconnectivity, and tortuosity in polymers. To our best knowledge, the present study is the first application of this strategy for analyzing the nanoscale porosity of MIPs. MIPs imprinted for propranolol - and the corresponding NIPs - were investigated establishing FIB/SEM tomography as a viable future strategy complementing conventional isotherm studies. For visualizing and understanding the properties of pore networks in detail, polymer particles were stained with osmium tetroxide (OsO 4 ) vapor, and embedded in epoxy resin. Staining with OsO 4 provides excellent contrast during high-resolution SEM imaging. After optimizing the threshold to discriminate between the stained polymer matrix, and pores filled with epoxy resin, a 3D model of the sampled volume may be established for deriving not only the pore volume and pore surface area, but also to visualize the interconnectivity and tortuosity of the pores within the sampled polymer volume. Detailed studies using different types of cross-linkers and the effect of hydrolysis on the resulting polymer properties have been investigated. In comparison of MIP and NIP, it could be unambiguously shown that the interconnectivity of the visualized pores in MIPs is significantly higher vs. the non-imprinted polymer, and that the pore volume and pore area is 34% and approx. 35% higher within the MIP matrix. This confirms that the templating process not only induces selective binding sites, but indeed also affects the physical properties of such polymers down to the nanoscale, and that additional chemical modification, e.g., via hydrolysis clearly affects that nature of the polymer.