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Sample records for network silsesquioxane polymers

  1. Polyhedral oligomeric silsesquioxane grafted polymer in polymeric foam

    DOEpatents

    King, Bruce A.; Patankar, Kshitish A.; Costeux, Stephane; Jeon, Hyun K.

    2017-01-17

    A polymeric foam article with a polymer matrix defining multiple cells therein has a polymer component with a first polymer that is a polyhedral oligomeric silsesquioxane grafted polymer that has a weight-average molecular weight of two kilograms per mole or higher and 200 kilograms per mole or lower.

  2. Polyhedral Oligomeric Silsesquioxane (POSS)-Containing Polymer Nanocomposites

    PubMed Central

    Ayandele, Ebunoluwa; Sarkar, Biswajit; Alexandridis, Paschalis

    2012-01-01

    Hybrid materials with superior structural and functional properties can be obtained by incorporating nanofillers into polymer matrices. Polyhedral oligomeric silsesquioxane (POSS) nanoparticles have attracted much attention recently due to their nanometer size, the ease of which these particles can be incorporated into polymeric materials and the unique capability to reinforce polymers. We review here the state of POSS-containing polymer nanocomposites. We discuss the influence of the incorporation of POSS into polymer matrices via chemical cross-linking or physical blending on the structure of nanocomposites, as affected by surface functional groups, and the POSS concentration. PMID:28348318

  3. Developments in Nanoscience: Polyhedral Oligomeric Silsesquioxane (POSS) - Polymers

    DTIC Science & Technology

    2006-05-31

    wt% POSS. a b 0 5 10 15 20 25 30 0.01 0.1 1 00 5 10 15 20 25 30 0 2 4 6 8 10 Approved for public release; distribution is unlimited 37 TABLES Air...DATE 08 MAR 2004 2 . REPORT TYPE 3. DATES COVERED - 4. TITLE AND SUBTITLE Developments in Nanoscience: Polyhedral Oligomeric Silsesquioxane (POSS...distribution is unlimited 2 Abstract This review is intended to cover the more recent advances in both structure-property relationships of polymers

  4. Cyclization Phenomena in the Sol-Gel Polymerization of a,w-Bis(triethoxysilyl)alkanes and Incorporation of the Cyclic Structures into Network Silsesquioxane Polymers

    SciTech Connect

    Alam, T.M.; Carpenter, J.P.; Dorhout, P.K.; Greaves, J.; Loy, D.A.; Shaltout, R.; Shea, K.J.; Small, J.H.

    1999-01-04

    Intramolecular cyclizations during acid-catalyzed, sol-gel polymerizations of ct,co- bis(tietioxysilyl)aWmes substintidly lengtien gelties formonomers witietiylene- (l), propylene- (2), and butylene-(3)-bridging groups. These cyclizations reactions were found, using mass spectrometry and %i NMR spectroscopy, to lead preferentially to monomeric and dimeric products based on six and seven membered disilsesquioxane rings. 1,2- Bis(triethoxysilyl)ethane (1) reacts under acidic conditions to give a bicyclic drier (5) that is composed of two annelated seven membered rings. Under the same conditions, 1,3- bis(triethoxysilyl)propane (2), 1,4-bis(triethoxysilyl)butane (3), and z-1,4- bis(triethoxysilyl)but-2-ene (10) undergo an intramolecular condensation reaction to give the six membemd and seven membered cyclic disilsesquioxanes 6, 7, and 11. Subsequently, these cyclic monomers slowly react to form the tricyclic dirners 8,9 and 12. With NaOH as polymerization catalyst these cyclic silsesquioxanes readily ~aeted to afford gels that were shown by CP MAS z%i NMR and infr=d spectroscopes to retain some cyclic structures. Comparison of the porosity and microstructwe of xerogels prepared from the cyclic monomers 6 and 7 with gels prepared directly from their acyclic precursors 2 and 3, indicate that the final pore structure of the xerogels is markedly dependent on the nature of the precursor. In addition, despite the fact that the monomeric cyclic disilsesquioxane species can not be isolated from 1-3 under basic conditions due to their rapid rate of gelation, spectroscopic techniques also detected the presence of the cyclic structures in the resulting polymeric gels.

  5. Understanding Controls on Wetting at Fluorinated Polyhedral Oligomeric Silsesquioxane/Polymer Surfaces.

    PubMed

    Ye, Yi; Tian, Ming; Zhang, Chen; Du, Zhongjie; Mi, Jianguo

    2016-01-12

    Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) nanoparticles have been widely used to enhance the hydrophobicity or oleophobicity of polymer films via constructing the specific micro/nanoscale roughness. In this work, we study the oleophobicity of pure and F-POSS-decorated poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) films using a dynamic density functional theory approach. The role of nanoparticle size and coverage and the chemical features of F-POSS and the polymer film in the wetting behavior of diiodomethane droplets has been integrated to the remaining ratio of surface potential to quantitatively characterize the corner effect. It is shown that, on the basis of universal force field parameters, the theoretically predicted contact angles are in general agreement with the available experimental data.

  6. Dispersion states and surface characteristics of physically blended polyhedral oligomeric silsesquioxane/polymer hybrid nanocomposites

    NASA Astrophysics Data System (ADS)

    Misra, Rahul

    Control of dispersion and segregation states of nanostructured additives is one of the biggest challenges in realizing the optimum potential of high performance hybrid polymer nanocomposites. Polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals, with their hybrid organic-inorganic nature and flexible functionalization with a variety of organic substituents, yield possibilities to control dispersion and tune compatibility in a wide range of polymer systems. The overall goal of this research is to investigate the fundamental parameters that influence the dispersion and segregation states of POSS nanostructured chemicals, and to understand chain dynamics and conformations in physically blended POSS hybrid polymer nanocomposites (HPNC's). Multiple structural and mechanical factors influencing macro to nano scale surface and bulk properties were successfully investigated and correlated. A strategy based on thermodynamic principles for selective control of POSS dispersion states in a given polymer matrix is developed and discussed. This dissertation consists of eight chapters. Chapter 1 provides a detailed introduction about the development and current research interest in POSS/polymer nanocomposites. This chapter also discusses limitations of current advanced nanoprobe techniques. Chapter 2 establishes the overall goal of this research and specific research ii objectives. Chapter 3 establishes the preferential surface migration behavior of physically dispersed, non-reactive, closed cage octaisobutyl POSS (Oib-POSS) in a non-polar polypropylene matrix. Furthermore, influence of POSS surface segregation on the surface properties, especially nano-tribomechanical behavior is also discussed. Chapter 4 expands the studies by melt blending two different types of POSS molecules, a non-reactive, closed cage Oib-POSS and an open cage trisilanolphenyl POSS (Tsp-POSS), in a nylon 6 matrix. This chapter discusses the morphology, nano-dispersion and macro- to

  7. Coatings of molecularly imprinted polymers based on polyhedral oligomeric silsesquioxane for open tubular capillary electrochromatography.

    PubMed

    Zhao, Qing-Li; Zhou, Jin; Zhang, Li-Shun; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-05-15

    Polyhedral oligomeric silsesquioxane (POSS) was successfully applied, for the first time, to prepare imprinted monolithic coating for capillary electrochromatography. The imprinted monolithic coating was synthesized with a mixture of PSS-(1-Propylmethacrylate)-heptaisobutyl substituted (MA 0702), S-amlodipine (template), methacrylic acid (functional monomer), and 2-methacrylamidopropyl methacrylate (crosslinker), in a porogenic mixture of toluene-isooctane. The influence of synthesis parameters on the imprinting effect and separation performance, including the amount of MA 0702, the ratio of template to monomer, and the ratio of monomer to crosslinker, was investigated. The greatest resolution for enantiomers separation on the imprinted monolithic column prepared with MA 0702 was up to 22.3, about 2 times higher than that prepared in absence of the POSS. Column efficiency on the POSS-based MIP coatings was beyond 30,000 plate m(-1). The comparisons between MIP coating synthesized with the POSS and without the POSS were made in terms of selectivity, column efficiency, and resolution. POSS-based MIP capillaries with naproxen or zopiclone was also prepared and separation of enantiomers can be achieved.

  8. Silsesquioxane-derived ceramic fibres

    NASA Technical Reports Server (NTRS)

    Hurwitz, F. I.; Farmer, S. C.; Terepka, F. M.; Leonhardt, T. A.

    1991-01-01

    Fibers formed from blends of silsesquioxane polymers were characterized to study the pyrolytic conversion of these precursors to ceramics. The morphology of fibers pyrolyzed to 1400 C revealed primarily amorphous glasses whose conversion to beta-SiC is a function of both blend composition and pyrolysis conditions. Formation of beta-SiC crystallites within the glassy phase is favored by higher than stoichiometric C/Si ratios, while carbothermal reduction of Si-O bonds to form SiC with loss of SiO and CO occurs at higher methyl/phenylpropyl silsesquioxane (lower C/Si) ratios. As the carbothermal reduction is assumed to be diffusion controlled, the fibers can serve as model systems to gain understanding of the silsesquioxane pyrolysis behavior, and therefore are useful in the development of polysilsesquioxane-derived ceramic matrices and coatings as well.

  9. Advanced Polymer Network Structures

    DTIC Science & Technology

    2016-02-01

    13. SUPPLEMENTARY NOTES 14. ABSTRACT Polymer networks and gels are important classes of materials for defense applications . In an effort to......it is no longer needed. Do not return it to the originator. ARL-TR-7612 ● FEB 2016 US Army Research Laboratory Advanced Polymer

  10. Simulated Associating Polymer Networks

    NASA Astrophysics Data System (ADS)

    Billen, Joris

    Telechelic associating polymer networks consist of polymer chains terminated by endgroups that have a different chemical composition than the polymer backbone. When dissolved in a solution, the endgroups cluster together to form aggregates. At low temperature, a strongly connected reversible network is formed and the system behaves like a gel. Telechelic networks are of interest since they are representative for biopolymer networks (e.g. F-actin) and are widely used in medical applications (e.g. hydrogels for tissue engineering, wound dressings) and consumer products (e.g. contact lenses, paint thickeners). In this thesis such systems are studied by means of a molecular dynamics/Monte Carlo simulation. At first, the system in rest is studied by means of graph theory. The changes in network topology upon cooling to the gel state, are characterized. Hereto an extensive study of the eigenvalue spectrum of the gel network is performed. As a result, an in-depth investigation of the eigenvalue spectra for spatial ER, scale-free, and small-world networks is carried out. Next, the gel under the application of a constant shear is studied, with a focus on shear banding and the changes in topology under shear. Finally, the relation between the gel transition and percolation is discussed.

  11. Surface modification of a polyhedral oligomeric silsesquioxane poly(carbonate-urea) urethane (POSS-PCU) nanocomposite polymer as a stent coating for enhanced capture of endothelial progenitor cells

    PubMed Central

    Tan, Aaron; Farhatnia, Yasmin; Goh, Debbie; G, Natasha; de Mel, Achala; Lim, Jing; Teoh, Swee-Hin; Malkovskiy, Andrey V; Chawla, Reema; Rajadas, Jayakumar; Cousins, Brian G; Hamblin, Michael R; Alavijeh, Mohammad S; Seifalian, Alexander M

    2013-01-01

    An unmet need exists for the development of next-generation multifunctional nanocomposite materials for biomedical applications, particularly in the field of cardiovascular regenerative biology. Herein, we describe the preparation and characterization of a novel polyhedral oligomeric silsesquioxane poly(carbonate-urea) urethane (POSS-PCU) nanocomposite polymer with covalently attached anti-CD34 antibodies to enhance capture of circulating endothelial progenitor cells (EPC). This material may be used as a new coating for bare metal stents used after balloon angioplasty to improve re-endothelialization. Biophysical characterization techniques were used to assess POSS-PCU and its subsequent functionalization with anti-CD34 antibodies. Results indicated successful covalent attachment of anti-CD34 antibodies on the surface of POSS-PCU leading to an increased propensity for EPC capture, whilst maintaining in vitro biocompatibility and hemocompatibility. POSS-PCU has already been used in 3 first-in-man studies, as a bypass graft, lacrimal duct and a bioartificial trachea. We therefore postulate that its superior biocompatibility and unique biophysical properties would render it an ideal candidate for coating medical devices, with stents as a prime example. Taken together, anti-CD34 functionalized POSS-PCU could form the basis of a nano-inspired polymer platform for the next generation stent coatings. PMID:24706135

  12. Flows in Polymer Networks

    NASA Astrophysics Data System (ADS)

    Tanaka, Fumihiko

    A simple transient network model is introduced to describe creation and annihilation of junctions in the networks of associating polymers. Stationary non-linear viscosity is calculated by the theory and by Monte Carlo simulation to study shear thickening. The dynamic mechanical moduli are calculated as functions of the frequency and the chain disengagement rate. From the peak of the loss modulus, the lifetime τx of the junction is estimated, and from the high frequency plateau of the storage modulus, the number of elastically effective chains in the network is found. Transient phenomena such as stress relaxation and stress overshoot are also theoretically studied. Results are compared with the recent experimental reports on the rheological study of hydrophobically modified water-soluble polymeters.

  13. Gold nanoparticles hosted in a water-soluble silsesquioxane polymer applied as a catalytic material onto an electrochemical sensor for detection of nitrophenol isomers.

    PubMed

    Silva, Paulo Sérgio da; Gasparini, Bianca C; Magosso, Hérica A; Spinelli, Almir

    2014-05-30

    The water-soluble 3-n-propyl-4-picolinium silsesquioxane chloride (Si4Pic(+)Cl(-)) polymer was prepared, characterized and used as a stabilizing agent for the synthesis of gold nanoparticles (nAu). The ability of Si4Pic(+)Cl(-) to adsorb anionic metal complexes such as AuCl4(-) ions allowed well-dispersed nAu to be obtained with an average particle size of 4.5nm. The liquid suspension of nAu-Si4Pic(+)Cl(-) was deposited by the drop coating method onto a glassy carbon electrode (GCE) surface to build a sensor (nAu-Si4Pic(+)Cl(-)/GCE) which was used for the detection of o-nitrophenol (o-NP) and p-nitrophenol (p-NP). Under optimized experimental conditions the reduction peak current increased with increasing concentrations of both nitrophenol isomers in the range of 0.1-1.5μmolL(-1). The detection limits were 46nmolL(-1) and 55nmolL(-1) for o-NP and p-NP, respectively. These findings indicate that the nAu-Si4Pic(+)Cl(-) material is a very promising candidate to assemble electrochemical sensors for practical applications in the field of analytical chemistry.

  14. Comparison of the bacterial removal performance of silver nanoparticles and a polymer based quaternary amine functiaonalized silsesquioxane coated point-of-use ceramic water filters.

    PubMed

    Zhang, Hongyin; Oyanedel-Craver, Vinka

    2013-09-15

    This study compares the disinfection performance of ceramic water filters impregnated with two antibacterial compounds: silver nanoparticles and a polymer based quaternary amine functiaonalized silsesquioxane (poly(trihydroxysilyl) propyldimethyloctadecyl ammonium chloride (TPA)). This study evaluated these compounds using ceramic disks manufactures with clay obtained from a ceramic filter factory located in San Mateo Ixtatan, Guatemala. Instead of using full size ceramic water filters, manufactured 6.5 cm diameter ceramic water filter disks were used. Results showed that TPA can achieve a log bacterial reduction value of 10 while silver nanoparticles reached up to 2 log reduction using a initial concentration of bacteria of 10(10)-10(11)CFU/ml. Similarly, bacterial transport demonstrated that ceramic filter disks painted with TPA achieved a bacterial log reduction value of 6.24, which is about 2 log higher than the values obtained for disks painted with silver nanoparticles (bacterial log reduction value: 4.42). The release of both disinfectants from the ceramic materials to the treated water was determined measuring the effluent concentrations in each test performed. Regarding TPA, about 3% of the total mass applied to the ceramic disks was released in the effluent over 300 min, which is slightly lower than the release percentage for silver nanoparticles (4%). This study showed that TPA provides a comparable disinfection performance than silver nanoparticles in ceramic water filter. Another advantage of using TPA is the cost as the price of TPA is considerable lower than silver nanoparticles. In spite of the use of TPA in several medical related products, there is only partial information regarding the health risk associated with the ingestion of this compound. Additional long-term toxicological information for TPA should be evaluated before its future application in ceramic water filters.

  15. Structural Evolution of Silica Gel and Silsesquioxane Using Thermal Curing.

    PubMed

    Hu, Nan; Rao, YuanQiao; Sun, Shengtong; Hou, Lei; Wu, Peiyi; Fan, Shaojuan; Ye, Bangjiao

    2016-08-01

    The curing of coatings of two types of siloxane containing materials, silica gel and silsesquioxane, at a modest temperature (<280℃) was studied with in situ heating Fourier transform infrared spectroscopy (FT-IR) in combination with perturbation correlation moving window (PCMW) and two-dimensional correlation spectroscopy (2D-COS) analyses. The result revealed detailed structural evolution of these two different gels. When the silica gel was heated, (Si-O)6 rings appeared from the random Si-O-Si network formed after sol gel reaction, followed by condensation of silanol groups. Upon further heating, the existing (Si-O)4 rings were broken down and converted into (Si-O)6 structures, and finally isolated silanols appeared. The transition from (Si-O)4 rings to (Si-O)6 rings was observed by IR and further confirmed with positron annihilation lifetime spectroscopy (PALS). In comparison, during the curing of hybrid silsesquioxane, the condensation of silanols happens immediately upon heating without the rearrangement of Si-O-Si network. Afterwards, the fraction of (Si-O)6 ring structure increased. (Si-O)4 structures exhibited higher stability in hybrid silsesquioxanes. In addition, the amount of silanols in silsesquioxane continued to reduce without the generation of isolated silanol in the end. The different curing behavior of silsesquioxanes from silica gel originates from the organic groups in silsesquioxanes, which lowers the cross-linking density and reduces the rigidity of siloxane network.

  16. Polymer network stretching during electrospinning

    NASA Astrophysics Data System (ADS)

    Greenfeld, Israel; Arinstein, Arkadii; Fezzaa, Kamel; Rafailovich, Miriam; Zussman, Eyal

    2011-03-01

    Fast X-ray phase contrast imaging is used to observe the flow of a semi-dilute polyethylene oxide solution during electrospinning. Micron-size glass particles mixed in the polymer solution allow viewing of the jet flow field, and reveal a high-gradient flow that has both longitudinal and radial components that grow rapidly along the jet. The resulting hydrodynamic forces cause substantial longitudinal stretching and transversal contraction of the polymer network within the jet, as confirmed by random walk simulation and theoretical modeling. The polymer network therefore concentrates towards the jet center, and its conformation may transform from a free state to a fully-stretched state within a short distance from the jet start. We acknowledge the financial support of the United States - Israel Bi-National Science Foundation (grant 2006061).

  17. Polymer networks: Modeling and applications

    NASA Astrophysics Data System (ADS)

    Masoud, Hassan

    Polymer networks are an important class of materials that are ubiquitously found in natural, biological, and man-made systems. The complex mesoscale structure of these soft materials has made it difficult for researchers to fully explore their properties. In this dissertation, we introduce a coarse-grained computational model for permanently cross-linked polymer networks than can properly capture common properties of these materials. We use this model to study several practical problems involving dry and solvated networks. Specifically, we analyze the permeability and diffusivity of polymer networks under mechanical deformations, we examine the release of encapsulated solutes from microgel capsules during volume transitions, and we explore the complex tribological behavior of elastomers. Our simulations reveal that the network transport properties are defined by the network porosity and by the degree of network anisotropy due to mechanical deformations. In particular, the permeability of mechanically deformed networks can be predicted based on the alignment of network filaments that is characterized by a second order orientation tensor. Moreover, our numerical calculations demonstrate that responsive microcapsules can be effectively utilized for steady and pulsatile release of encapsulated solutes. We show that swollen gel capsules allow steady, diffusive release of nanoparticles and polymer chains, whereas gel deswelling causes burst-like discharge of solutes driven by an outward flow of the solvent initially enclosed within a shrinking capsule. We further demonstrate that this hydrodynamic release can be regulated by introducing rigid microscopic rods in the capsule interior. We also probe the effects of velocity, temperature, and normal load on the sliding of elastomers on smooth and corrugated substrates. Our friction simulations predict a bell-shaped curve for the dependence of the friction coefficient on the sliding velocity. Our simulations also illustrate

  18. Network dynamics in nanofilled polymers

    PubMed Central

    Baeza, Guilhem P.; Dessi, Claudia; Costanzo, Salvatore; Zhao, Dan; Gong, Shushan; Alegria, Angel; Colby, Ralph H.; Rubinstein, Michael; Vlassopoulos, Dimitris; Kumar, Sanat K.

    2016-01-01

    It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams–Landel–Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ∼31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which ‘tie' NPs together into a network. PMID:27109062

  19. Network dynamics in nanofilled polymers

    NASA Astrophysics Data System (ADS)

    Baeza, Guilhem P.; Dessi, Claudia; Costanzo, Salvatore; Zhao, Dan; Gong, Shushan; Alegria, Angel; Colby, Ralph H.; Rubinstein, Michael; Vlassopoulos, Dimitris; Kumar, Sanat K.

    2016-04-01

    It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams-Landel-Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ~31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which `tie' NPs together into a network.

  20. High performance shape memory polymer networks based on rigid nanoparticle cores

    PubMed Central

    Song, Jie

    2010-01-01

    Smart materials that can respond to external stimuli are of widespread interest in biomedical science. Thermal-responsive shape memory polymers, a class of intelligent materials that can be fixed at a temporary shape below their transition temperature (Ttrans) and thermally triggered to resume their original shapes on demand, hold great potential as minimally invasive self-fitting tissue scaffolds or implants. The intrinsic mechanism for shape memory behavior of polymers is the freezing and activation of the long-range motion of polymer chain segments below and above Ttrans, respectively. Both Ttrans and the extent of polymer chain participation in effective elastic deformation and recovery are determined by the network composition and structure, which are also defining factors for their mechanical properties, degradability, and bioactivities. Such complexity has made it extremely challenging to achieve the ideal combination of a Ttrans slightly above physiological temperature, rapid and complete recovery, and suitable mechanical and biological properties for clinical applications. Here we report a shape memory polymer network constructed from a polyhedral oligomeric silsesquioxane nanoparticle core functionalized with eight polyester arms. The cross-linked networks comprising this macromer possessed a gigapascal-storage modulus at body temperature and a Ttrans between 42 and 48 °C. The materials could stably hold their temporary shapes for > 1 year at room temperature and achieve full shape recovery ≤ 51 °C in a matter of seconds. Their versatile structures allowed for tunable biodegradability and biofunctionalizability. These materials have tremendous promise for tissue engineering applications. PMID:20375285

  1. 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.

  2. Nanoscale glucan polymer network causes pathogen resistance.

    PubMed

    Eggert, Dennis; Naumann, Marcel; Reimer, Rudolph; Voigt, Christian A

    2014-02-24

    Successful defence of plants against colonisation by fungal pathogens depends on the ability to prevent initial penetration of the plant cell wall. Here we report that the pathogen-induced (1,3)-β-glucan cell wall polymer callose, which is deposited at sites of attempted penetration, directly interacts with the most prominent cell wall polymer, the (1,4)-β-glucan cellulose, to form a three-dimensional network at sites of attempted fungal penetration. Localisation microscopy, a super-resolution microscopy technique based on the precise localisation of single fluorescent molecules, facilitated discrimination between single polymer fibrils in this network. Overexpression of the pathogen-induced callose synthase PMR4 in the model plant Arabidopsis thaliana not only enlarged focal callose deposition and polymer network formation but also resulted in the exposition of a callose layer on the surface of the pre-existing cellulosic cell wall facing the invading pathogen. The importance of this previously unknown polymeric defence network is to prevent cell wall hydrolysis and penetration by the fungus. We anticipate our study to promote nanoscale analysis of plant-microbe interactions with a special focus on polymer rearrangements in and at the cell wall. Moreover, the general applicability of localisation microscopy in visualising polymers beyond plant research will help elucidate their biological function in complex networks.

  3. Nanoscale glucan polymer network causes pathogen resistance

    PubMed Central

    Eggert, Dennis; Naumann, Marcel; Reimer, Rudolph; Voigt, Christian A.

    2014-01-01

    Successful defence of plants against colonisation by fungal pathogens depends on the ability to prevent initial penetration of the plant cell wall. Here we report that the pathogen-induced (1,3)-β-glucan cell wall polymer callose, which is deposited at sites of attempted penetration, directly interacts with the most prominent cell wall polymer, the (1,4)-β-glucan cellulose, to form a three-dimensional network at sites of attempted fungal penetration. Localisation microscopy, a super-resolution microscopy technique based on the precise localisation of single fluorescent molecules, facilitated discrimination between single polymer fibrils in this network. Overexpression of the pathogen-induced callose synthase PMR4 in the model plant Arabidopsis thaliana not only enlarged focal callose deposition and polymer network formation but also resulted in the exposition of a callose layer on the surface of the pre-existing cellulosic cell wall facing the invading pathogen. The importance of this previously unknown polymeric defence network is to prevent cell wall hydrolysis and penetration by the fungus. We anticipate our study to promote nanoscale analysis of plant-microbe interactions with a special focus on polymer rearrangements in and at the cell wall. Moreover, the general applicability of localisation microscopy in visualising polymers beyond plant research will help elucidate their biological function in complex networks. PMID:24561766

  4. Entanglement network in nanoparticle reinforced polymers.

    PubMed

    Riggleman, Robert A; Toepperwein, Gregory; Papakonstantopoulos, George J; Barrat, Jean-Louis; de Pablo, Juan J

    2009-06-28

    Polymer nanocomposites have been widely studied in efforts to engineer materials with mechanical properties superior to those of the pure polymer, but the molecular origins of the sought-after improved properties have remained elusive. An ideal polymer nanocomposite model has been conceived in which the nanoparticles are dispersed throughout the polymeric matrix. A detailed examination of topological constraints (or entanglements) in a nanocomposite glass provides new insights into the molecular origin of the improved properties in polymer nanocomposites by revealing that the nanoparticles impart significant enhancements to the entanglement network. Nanoparticles are found to serve as entanglement attractors, particularly at large deformations, altering the topological constraint network that arises in the composite material.

  5. Environmental memory of polymer networks under stress.

    PubMed

    Quitmann, Dominik; Gushterov, Nikola; Sadowski, Gabriele; Katzenberg, Frank; Tiller, Joerg C

    2014-06-04

    Generally reversible stimuli-responsive materials do not memorize the stimulus. In this study we describe an example in which stretched and constrained semi-crystalline polymer networks respond to solvent gases with stress and simultaneously memorize the concentration and the chemical nature of the solvent itself in their microstructure. This written solvent signature can even be deleted by temperature.

  6. Nonaffine rubber elasticity for stiff polymer networks.

    PubMed

    Heussinger, Claus; Schaefer, Boris; Frey, Erwin

    2007-09-01

    We present a theory for the elasticity of cross-linked stiff polymer networks. Stiff polymers, unlike their flexible counterparts, are highly anisotropic elastic objects. Similar to mechanical beams, stiff polymers easily deform in bending, while they are much stiffer with respect to tensile forces ("stretching"). Unlike in previous approaches, where network elasticity is derived from the stretching mode, our theory properly accounts for the soft bending response. A self-consistent effective medium approach is used to calculate the macroscopic elastic moduli starting from a microscopic characterization of the deformation field in terms of "floppy modes"-low-energy bending excitations that retain a high degree of nonaffinity. The length scale characterizing the emergent nonaffinity is given by the "fiber length" lf, defined as the scale over which the polymers remain straight. The calculated scaling properties for the shear modulus are in excellent agreement with the results of recent simulations obtained in two-dimensional model networks. Furthermore, our theory can be applied to rationalize bulk rheological data in reconstituted actin networks.

  7. Enabling Nanoparticle Networking in Semicrystalline Polymer Matrices

    SciTech Connect

    Kaur, Jasmeet; Lee, Ji Hoon; Bucknall, David G.; Shofner, Meisha L.

    2012-10-23

    Among the physical and chemical attributes of the nanocomposite components and their interactions that contribute to the ultimate material properties, nanoparticle arrangement in the matrix is a key contributing factor that has been targeted through materials choices and processing strategies in numerous previous studies. Often, the desired nanocomposite morphology contains individually dispersed and distributed nanoparticles. In this research, a phase-segregated morphology containing nanoparticle networks was studied. A model nanocomposite system composed of calcium phosphate nanoparticles and a poly(3-hydroxybutyrate) matrix was produced to understand how polymer crystallization and crystal structure can facilitate the formation of a phase-segregated morphology containing nanoparticle networks. Two chemically similar calcium phosphate nanoparticle systems with different shapes, near-spherical and nanofiber, were synthesized for use in the nanocomposites. The different shapes were used independently in nanocomposites in an attempt to understand the effect of the nanoparticle shapes on crystallization-mediated nanoparticle network formation. The resulting nanocomposites were characterized to establish the effects of component interactions on the polymer structure. Additionally from the viscoelastic properties, structure-property relationships in these materials can be defined as a function of nanoparticle shape and concentration. The results of this research suggest that when the nanocomposite components are not strongly interacting, polymer crystallization may be used as a forced assembly method for nanoparticle networks. Such a methodology has applications to the design of functional polymer nanocomposites such as biomedical implant materials and organic photovoltaic materials where judicious choice of nanoparticle-polymer pairs and control of polymer crystal nucleation and growth processes could be used to control the length scale of phase segregation.

  8. Biomimetic oral mucin from polymer micelle networks

    NASA Astrophysics Data System (ADS)

    Authimoolam, Sundar Prasanth

    -functional implant coats. KEYWORDS: Biomimic, Bioapplication, Drug delivery, Filomicelle, Mucin, Polymer networks.

  9. Conjugated polymer networks: Synthesis and properties

    NASA Astrophysics Data System (ADS)

    Kokil, Akshay

    The experimental research program that forms the basis of this thesis has been directed towards the design, synthesis, processing and physical characterization of well-defined conjugated polymer networks. It attempts to provide answers to the questions how such materials can be synthesized and processed and how the introduction of cross-links can be exploited for the creation of polymeric materials with optimized optic and electronic characteristics. Interestingly, this family of materials has received little attention in the past, at least as far as systematic studies of well-defined systems are concerned. This situation may be a direct consequence of the challenge to introduce conjugated cross-links into conjugated polymers and retain adequate processibility. We have shown that organometallic polymer networks based on linear conjugated polymers are readily accessible through ligand-exchange reactions. This approach was exemplified by exploiting the ethynyl moieties comprised in poly( p-phenylene ethynylene) (PPE) derivatives as ligand sites, which allow for complexation with selected metals and cross-linking via the resulting PPE-Metal complexes. Focusing on the dinuclear complex [Pt-(mu-Cl)Cl-PPE] 2 and PPE-Pt0 as crosslinks, we have conducted an in-depth investigation on how the nature of the metal cross-links influences the materials characteristics, in particular the charge transport properties. We first investigated the charge carrier mobility of poly[2,5-dioctyloxy-1,4-diethynyl-phenylene- alt-2,5-bis(2'-ethylhexyloxy)-1,4-phenylene] (EHO-OPPE), as a classic representative of poly(p-phenylene ethynylene) (PPE) derivatives, which represent an important class of conjugated polymers. In what appears to be the first study ever conducted on the mobility of any PPE, we found that EHO-OPPE displays ambipolar charge transport characteristics with very high electron (1.9·10-3 cm2V-1 s-1) and hole (1.6·10-3 cm 2V-1s-1) mobilities. Most importantly, the introduction

  10. Entanglement effects in model polymer networks

    NASA Astrophysics Data System (ADS)

    Everaers, R.; Kremer, K.

    The influence of topological constraints on the local dynamics in cross-linked polymer melts and their contribution to the elastic properties of rubber elastic systems are a long standing problem in statistical mechanics. Polymer networks with diamond lattice connectivity (Everaers and Kremer 1995, Everaers and Kremer 1996a) are idealized model systems which isolate the effect of topology conservation from other sources of quenched disorder. We study their behavior in molecular dynamics simulations under elongational strain. In our analysis we compare the measured, purely entropic shear moduli G to the predictions of statistical mechanical models of rubber elasticity, making extensive use of the microscopic structural and topological information available in computer simulations. We find (Everaers and Kremer 1995) that the classical models of rubber elasticity underestimate the true change in entropy in a deformed network significantly, because they neglect the tension along the contour of the strands which cannot relax due to entanglements (Everaers and Kremer (in preparation)). This contribution and the fluctuations in strained systems seem to be well described by the constrained mode model (Everaers 1998) which allows to treat the crossover from classical rubber elasticity to the tube model for polymer networks with increasing strand length within one transparant formalism. While this is important for the description of the effects we try to do a first quantitative step towards their explanation by topological considerations. We show (Everaers and Kremer 1996a) that for the comparatively short strand lengths of our diamond networks the topology contribution to the shear modulus is proportional to the density of entangled mesh pairs with non-zero Gauss linking number. Moreover, the prefactor can be estimated consistently within a rather simple model developed by Vologodskii et al. and by Graessley and Pearson, which is based on the definition of an entropic

  11. Silsesquioxanes as precursors to ceramic composites

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Hyatt, Lizbeth H.; Gorecki, Joy; Damore, Lisa

    1987-01-01

    Silsesquioxanes having the general structure RSiO sub 1.5, where R = methyl, propyl, or phenyl, melt flow at 70 to 100 C. Above 100 C, free -OH groups condense. At 225 C further crosslinking occurs, and the materials form thermosets. Pyrolysis, with accompanying loss of volatiles, takes place at nominally 525 C. At higher temperatures, the R group serves as an internal carbon soruce for carbo-thermal reduction to SiC accompanied by the evolution of CO. By blending silsesquioxanes with varying R groups, both the melt rheology and composition of the fired ceramic can be controlled. Fibers can be spun from the melt which are stable in argon in 1400 C. The silsesquioxanes also were used as matrix precursors for Nicalon and alpha-SiC platelet reinforced composites.

  12. Molecular modeling of amorphous, non-woven polymer networks.

    PubMed

    Krausse, Constantin A; Milek, Theodor; Zahn, Dirk

    2015-10-01

    We outline a simple and efficient approach to generating molecular models of amorphous polymer networks. Similar to established techniques of preparing woven polymer networks from quenching high-temperature molecular simulation runs, we use a molecular dynamics simulations of a generic melt as starting points. This generic melt is however only used to describe parts of the polymers, namely the cross-linker units which positions are adopted from particle positions of the quenched melt. Specific degrees of network connectivity are tuned by geometric criteria for linker-linker connections and by suitable multi-body interaction potentials applied to the generic melt simulations. Using this technique we demonstrate adjusting fourfold linker coordination in amorphous polymer networks comprising 10-20% under-coordinated linkers. Graphical Abstract Molecular modeling of amorphous, non-woven polymer networks.

  13. Silsesquioxane-based 193 nm bilayer resists: characterization and lithographic evaluation

    NASA Astrophysics Data System (ADS)

    Ito, Hiroshi; Truong, Hoa D.; Burns, Sean D.; Pfeiffer, Dirk; Huang, Wu-Song; Khojasteh, Mahmoud M.; Varanasi, P. Rao; Lercel, Mike

    2005-05-01

    Polysilsesquioxane-based 193 nm positive bilayer resists are described. In this design Si for etch resistance is placed in every repeat unit and acid-labile protected and acidic groups (and polar units) are in the side chain, allowing to incorporate each lithographically critical functionality in sufficient quantity. Fluoroalcohol is employed as an acid group instead of carboxylic acid because of its more attractive dissolution properties. Polymers were carefully analyzed by 19F, 13C, and 29Si NMR to determine composition and to quantify residual acetyl, silanol, and Q/T. Hydrogen-bonding between tertiary ester and fluoroalcohol in the polysilsesquioxanes was investigated by FT-IR and the effect of lactone incorporation on the thermal deprotection temperature elucidated. In order to better understand the dissolution behavior of exposed resist films, the silsesquioxane resist polymers were partially (ca. 30%) and fully deprotected in solution with acid and their dissolution kinetics investigated by using a quartz crystal microbalance (QCM). It has been found that the exposed areas of the silsesquioxane resists can have a very fast dissolution rate (Rmax) of >20,000 A/sec (or even >100,000 A/sec). Heating the fully deprotected model polymers to 150°C did not reduce the dissolution rate much, suggesting thermal condensation of silanol end groups is insignificant. Model deprotected polymers containing triphenylsulfonium nonaflate were exposed to 254 nm radiation, baked, and subjected to QCM measurements in order to determine whether or not acid-catalyzed silanol condensation would reduce the dissolution rate. A combination of high dose and high temperature bake resulted in significant reduction of the dissolution rate in the silsesquioxane polymer containing a small trifluoroalcohol. However, the dissolution behavior of the polymer bearing a bulky norbornene hexafluoroalcohol was unaffected by exposure and bake. Chemical and development contrast curves were generated

  14. Covalently crosslinked diels-alder polymer networks.

    SciTech Connect

    Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John

    2011-09-01

    This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.

  15. Interpenetrating polymer networks from acetylene terminated materials

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Hergenrother, P. M.

    1989-01-01

    As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

  16. Relaxation dynamics of a multihierarchical polymer network

    NASA Astrophysics Data System (ADS)

    Jurjiu, Aurel; Biter, Teodor Lucian; Turcu, Flaviu

    2017-01-01

    In this work, we study the relaxation dynamics of a multihierarchical polymer network built by replicating the Vicsek fractal in dendrimer shape. The relaxation dynamics is investigated in the framework of the generalized Gaussian structure model by employing both Rouse and Zimm approaches. In the Rouse-type approach, we show the iterative procedure whereby the whole eigenvalue spectrum of the connectivity matrix of the multihierarchical structure can be obtained. Remarkably, the general picture that emerges from both approaches, even though we have a mixed growth algorithm, is that the obtained multihierarchical structure preserves the individual relaxation behaviors of its components. The theoretical findings with respect to the splitting of the intermediate domain of the relaxation quantities are well supported by experimental results.

  17. Mesoscopic Simulations of Crosslinked Polymer Networks

    NASA Astrophysics Data System (ADS)

    Megariotis, Grigorios; Vogiatzis, Georgios G.; Schneider, Ludwig; Müller, Marcus; Theodorou, Doros N.

    2016-08-01

    A new methodology and the corresponding C++ code for mesoscopic simulations of elastomers are presented. The test system, crosslinked ds-1’4-polyisoprene’ is simulated with a Brownian Dynamics/kinetic Monte Carlo algorithm as a dense liquid of soft, coarse-grained beads, each representing 5-10 Kuhn segments. From the thermodynamic point of view, the system is described by a Helmholtz free-energy containing contributions from entropic springs between successive beads along a chain, slip-springs representing entanglements between beads on different chains, and non-bonded interactions. The methodology is employed for the calculation of the stress relaxation function from simulations of several microseconds at equilibrium, as well as for the prediction of stress-strain curves of crosslinked polymer networks under deformation.

  18. Hydrophobic Silsesquioxane Nanoparticles and Nanocomposite Surfaces (POSTPRINT)

    DTIC Science & Technology

    2006-05-04

    Fluorinated Polyhedral Oligomeric Silsesquioxanes are hydrophobic nanoparticles. One compound, FD8T8, is ultrahydrophobic, possessing a water contact ... angle of 154 deg. This is believed to be the most hydrophobic and lowest surface tension crystalline substance known. Analysis of the x-ray crystal

  19. Oxovanadium(IV) silsesquioxane complexes.

    PubMed

    Ohde, Christian; Limberg, Christian; Stösser, Reinhard; Demeshko, Serhiy

    2010-03-01

    In the context of a potential modeling of reduced oxovanadium species occurring on the surfaces of silica-supported vanadia catalysts in the course of its turnover, the incompletely condensed silsesquioxane H(3)(c-pentyl)T(7) was reacted with Cl(4)V(THF)(2) (where THF = tetrahydrofuran) in the presence of triethylamine. Precipitation of 3 equiv of HNEt(3)Cl seemed to point to the clean formation of [((c-pentyl)T(7))(V(IV)Cl)] (1), which was supported by electron paramagnetic resonance studies performed for the resulting solutions, but further analytical and spectroscopic investigations showed that the processes occurring at that stage are more complex than that and even include the formation of [((c-pentyl)T(7))(V(V)O)](2) as a side product. Storage of a red-brown hexane solution of this product mixture reproducibly led to the precipitation of blue crystals belonging to the chloride-free compound [((c-pentyl)T(7))(2)(V(IV)=O)(3)(THF)(2)] (2), as revealed by single-crystal X-ray diffraction. Performing the same reaction in the presence of 2 equiv of pyridine leads to an analogous product, where the THF ligands are replaced by pyridine. Subsequent investigations showed that the terminal oxo ligands at the vanadium centers are, on the one hand, due to the presence of adventitious water; on the other hand, the [(c-pentyl)T(7)](3-) ligand also acted as a source of O(2-). The results of SQUID measurements performed for 2 can be interpreted in terms of a ferromagnetic coupling between the vanadyl units. Exposing 2 to a dioxygen atmosphere resulted in its immediate oxidation to yield the V(V) complex [((c-pentyl)T(7))(V(V)O)](2), which may model a fast reoxidation reaction of oxovanadium(IV) trimers on silica surfaces.

  20. Wavelength selective polymer network formation of end-functional star polymers.

    PubMed

    Kaupp, Michael; Hiltebrandt, Kai; Trouillet, Vanessa; Mueller, Patrick; Quick, Alexander S; Wegener, Martin; Barner-Kowollik, Christopher

    2016-01-31

    A wavelength selective technique for light-induced network formation based on two photo-active moieties, namely ortho-methylbenzaldehyde and tetrazole is introduced. The network forming species are photo-reactive star polymers generated via reversible activation fragmentation chain transfer (RAFT) polymerization, allowing the network to be based on almost any vinylic monomer. Direct laser writing (DLW) allows to form any complex three-dimensional structure based on the photo-reactive star polymers.

  1. Phase stability of weakly crosslinked interpenerating polymer networks

    NASA Technical Reports Server (NTRS)

    Binder, K.; Frisch, H. L.

    1984-01-01

    A phenomenological theory is formulated for chemically quenched binary interpenetrating polymer networks (IPNs), considering both simultaneously crosslinked networks and sequentially crosslinked networks, as well as pseudointerpenetrating networks (where only one component is crosslinked and the other is a linear polymer). The construction of free energy functionals for homogeneous weakly crosslinked IPNs and pseudo-IPNs and their spinodal curves and critical points of unmixing is described. These free energy functionals are augmented with gradient energy terms in order to consider effects due to spatially varying small inhomogeneities in the network chain concentration. The dynamic response and the initial spinodal decomposition of IPNs are discussed.

  2. Nanoparticle effect on polymer chain dynamics and entanglement network

    NASA Astrophysics Data System (ADS)

    Li, Ying; Kroger, Martin

    We investigated structure and dynamics of polymer nanocomposites through molecular modeling, by considering different molecular weights of polymers chains, and volume fractions of fillers. The dynamics of unentangled chains can be separated into two phases, a bulk polymer phase and a confined polymer phase between fillers. The dynamics of a confined polymer is slower than that of a bulk polymer, while still exhibiting high mobility. The amount of the bulk polymer phase is found to exponentially decay with increasing volume fraction of fillers. When highly entangled polymer chains are confined between fillers, their conformation and entanglement network are dramatically changed, in district with their unentangled counterparts. The entangled polymer chains are found to be significantly disentangled and flattened during increment of the volume fractions of spherical nonattractive fillers. A critical volume fraction is found to control the crossover from polymer chain entanglements to `nanoparticle entanglements', below which the polymer chain relaxation accelerates upon filling. These results provide a microscopic understanding of the dynamics of entangled polymer chains inside their composites, and offer an explanation for the unusual rheological properties of polymer composites. Supported by Department of Mechanical Engineering, University of Connecticut.

  3. Thermo-mechanical characterization of a monochlorophenyl, hepta isobutyl polyhedral oligomeric silsesquioxane/polystyrene composite

    SciTech Connect

    Blanco, Ignazio Bottino, Francesco A. Cicala, Gianluca Cozzo, Giulia Latteri, Alberta Recca, Antonino

    2014-05-15

    The thermal and mechanical properties of a monochlorophenyl, hepta isobutyl Polyhedral Oligomeric Silsesquioxane/Polystyrene (ph,hib-POSS/PS) composite were studied and compared with those of pristine polymer. ph,hib-POSS/PS system was prepared by solubilization and precipitation of Polystyrene (PS) in the presence of POSS. Scanning Electron Microscopy (SEM) was performed to check the distribution of the filler in the polymer matrix. Dynamic Mechanical Analysis (DMA) was carried out to measure viscoelastic properties of solid samples. Degradations were carried out into a thermobalance and the obtained thermogravimetric (TG) and differential thermogravimetric (DTG) curves were discussed and interpreted.

  4. Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

    SciTech Connect

    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.

  5. Polysiloxane Based Interpenetrating Polymer Networks: synthesis and Properties

    NASA Astrophysics Data System (ADS)

    Fichet, Odile; Vidal, Frédéric; Darras, Vincent; Boileau, Sylvie; Teyssié, Dominique

    This article summarizes a large amount of work carried out in our laboratory on polysiloxane based Interpenetrating Polymer Networks (IPNs). First, a polydimethylsiloxane (PDMS) network has been combined with a cellulose acetate butyrate (CAB) network in order to improve its mechanical properties. Second, a PDMS network was combined with a fluorinated polymer network. Thanks to a perfect control of the respective rates of formation of each network it has been possible to avoid polymer phase separation during the IPN synthesis. Physico-chemical analyses of these materials led to classify them as "true" IPNs according to Sperling's definition. In addition, synergy of the mechanical properties, on the one hand, and of the surface properties, on the other hand, was displayed.

  6. Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Wallace, C. J. (Inventor)

    1978-01-01

    An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.

  7. Porous networks derived from synthetic polymer-clay complexes

    SciTech Connect

    Carrado, K.A.; Thiyagarajan, P.; Elder, D.L.

    1995-05-12

    Synthetic hectorites were hydrothermally crystallized with direct incorporation of a cationic polymer poly(dimethyl diallyl ammonium chloride) (PDDA), and two neutral cellulosic polymers hydroxypropyl methylcellulose (HPMC) and hydroxyethyl cellulose (HEC). Synthetic PDDA-hectorite displays the lowest d-spacing at 15.8 {Angstrom} along with less polymer incorporation (7.8 wt % organic) than the neutral polymers (18--22 wt % organic). Thermal analysis and small angle neutron scattering were used to further examine the polymer-clay systems. Clay platelets of the largest size and best stacking order occur when cationic PDDA polymer is used. PDDA also enhances these properties over the crystallites prepared for a control mineral, where no polymer is used. HEC acts to aggregate the silica, leaving less to react to form clay. The clay platelets which result from HEC are small, not stacked to a large degree, and oriented randomly. Neutral HPMC acts more like cationic PDDA in that larger clay platelets are allowed to form. The extended microstructure of the clay network remains undisturbed after polymer is removed by calcination. When no polymer is used, the synthetic hectorite has a N{sub 2} BET surface area of 200 M{sup 2}/gm, even after calcination. This increases by 20--50% for the synthetic polymer-hectorites after the polymer is removed by calcination.

  8. Phase diagram of hopping conduction mechanisms in polymer nanofiber network

    SciTech Connect

    Li, Jeng-Ting; Lu, Yu-Cheng; Jiang, Shiau-Bin; Zhong, Yuan-Liang; Yeh, Jui-Ming

    2015-12-07

    Network formation by nanofiber crosslinking is usually in polymer materials as application in organic semiconductor devices. Electron hopping transport mechanisms depend on polymer morphology in network. Conducting polymers morphology in a random network structure is modeled by a quasi-one-dimensional system coupled of chains or fibers. We observe the varying hopping conduction mechanisms in the polyaniline nanofibers of the random network structure. The average diameter d of the nanofibers is varied from approximately 10 to 100 nm. The different dominant hopping mechanisms including Efros-Shklovskii variable-range hopping (VRH), Mott VRH, and nearest-neighbor hopping are dependent on temperature range and d in crossover changes. The result of this study is first presented in a phase diagram of hopping conduction mechanisms based on the theories of the random network model. The hopping conduction mechanism is unlike in normal semiconductor materials.

  9. Synthesis and Characterization of Polyfunctional Polyhedral Silsesquioxane Cages

    NASA Astrophysics Data System (ADS)

    Sulaiman, Santy

    Recent studies on octameric polyhedral silsesquioxanes, (RSiO1.5 )8, indicate that the silsesquioxane cage is not just a passive component but appears to be involved in electron delocalization with conjugated organic tethers in the excited state. This dissertation presents the synthesis and characterization of (RSiO1.5)8 molecules with unique photophysical properties that provide support for the existence of conjugation that involves the (RSiO1.5)8 cage. The dissertation first discusses the elaboration of octavinylsilsesquioxane via cross-metathesis to form styrenyl-functionalized octasilsesquioxane molecules. Subsequent Heck coupling reactions of p-bromostyrenyl derivative provides vinylstilbene-functionalized octasilsesquioxane. The amino derivative, NH2VinylStilbeneOS, show highly red-shifted emission spectrum (100 nm from the simple organic analog p-vinylstilbene) and high two-photon absorption (TPA) cross-section value (100 GM/moiety), indicating charge-transfer processes involving the silsesquioxane cage as the electron acceptor. The unique photophysical properties of polyfunctional luminescent cubic silsesquioxanes synthesized from ortho-8-, (2,5)-16-, and 24-brominated octaphenylsilsesquioxane (OPS) via Heck coupling show how the steric interactions of the organic tethers at the silsesquioxane cage corner affect conjugation with the silsesquioxane cage. Furthermore, the high TPA cross-section (10 GM/moiety) and photoluminescence quantum yield (20%) of OPS functionalized with 24 acetoxystyrenyl groups suggest that the existence excited states in these molecules with similar energies and decay rates: normal radiative pi- pi* transition and charge transfer involving the silsesquioxane cage. The fluoride ion-catalyzed rearrangement reactions of cage and polymeric silsesquioxanes provide a convenient route to a mixture of deca- and dodecameric silsesquioxane molecules in high yields, giving us the opportunity to investigate the effect of silsesquioxane cage

  10. Biocompatibility of Synthetic Poly(ester urethane)/Polyhedral Oligomeric Silsesquioxane Matrices with Embryonic Stem Cell Proliferation and Differentiation

    PubMed Central

    Guo, Yan-Lin; Wang, Wenshou; Otaigbe, Joshua U.

    2010-01-01

    Incorporation of polyhedral oligomeric silsesquioxanes (POSS) into poly (ester urethane)s (PEU) as a building block results in a PEU/POSS hybrid polymer with increased mechanical strength and thermostability. An attractive feature of the new polymer is that it forms a porous matrix when cast in the form of a thin film, making it potentially useful in tissue engineering. In this study, we present detailed microscopic analysis of the PEU/POSS matrix and demonstrate its biocompatibility with cell culture. The PEU/POSS polymer forms a continuous porous matrix with open pores and interconnected grooves. From SEM image analysis, it is calculated that there are about 950 pores per mm2 of the matrix area with pore size ranging from 1 to 15 μm in diameter. The area occupied by the pores represents approximately 7.6 % of matrix area. Using mouse embryonic stem cells (ESCs), we demonstrate that the PEU/POSS matrix provides excellent support for cell proliferation and differentiation. Under the cell culture condition optimized to maintain self-renewal, ESCs grown on a PEU/POSS matrix exhibit undifferentiated morphology, express pluripotency markers, and have similar growth rate to cells grown on gelatin. When induced for differentiation, ESCs underwent dramatic morphological change, characterized by the loss of clonogenecity and increased cell size with well-expanded cytoskeleton networks. Differentiated cells are able to form a continuous monolayer that is closely embedded on the matrix. The excellent compatibility between the PEU/POSS matrix and ESC proliferation/differentiation demonstrates the potential of using PEU/POSS polymers in future ESC-based tissue engineering. PMID:20213627

  11. Synthetic Oral Mucin Mimic from Polymer Micelle Networks

    PubMed Central

    2015-01-01

    Mucin networks are formed in the oral cavity by complexation of glycoproteins with other salivary proteins, yielding a hydrated lubricating barrier. The function of these networks is linked to their structural, chemical, and mechanical properties. Yet, as these properties are interdependent, it is difficult to tease out their relative importance. Here, we demonstrate the ability to recreate the fibrous like network through a series of complementary rinses of polymeric worm-like micelles, resulting in a 3-dimensional (3D) porous network that can be deposited layer-by-layer onto any surface. In this work, stability, structure, and microbial capture capabilities were evaluated as a function of network properties. It was found that network structure alone was sufficient for bacterial capture, even with networks composed of the adhesion-resistant polymer, poly(ethylene glycol). The synthetic networks provide an excellent, yet simple, means of independently characterizing mucin network properties (e.g., surface chemistry, stiffness, and pore size). PMID:24992241

  12. Hydrogen silsesquioxane mold coatings for improved replication of nanopatterns by injection molding

    NASA Astrophysics Data System (ADS)

    Hobæk, Thor Christian; Matschuk, Maria; Kafka, Jan; Pranov, Henrik J.; Larsen, Niels B.

    2015-03-01

    We demonstrate the replication of nanosized pillars in polymer (cyclic olefin copolymer) by injection molding using nanostructured thermally cured hydrogen silsesquioxane (HSQ) ceramic coatings on stainless steel mold inserts with mold nanostructures produced by a simple embossing process. At isothermal mold conditions, the average pillar height increases by up to 100% and a more uniform height distribution is observed compared to a traditional metal mold insert. Thermal heat transfer simulations predict that the HSQ film retards the cooling of the polymer melt during the initial stages of replication, thus allowing more time to fill the nanoscale cavities compared to standard metal molds. A monolayer of a fluorinated silane (heptadecafluorotrichlorosilane) deposited on the mold surface reduces the mold/polymer interfacial energy to support demolding of the polymer replica. The mechanical stability of thermally cured HSQ makes it a promising material for nanopattern replication on an industrial scale without the need for slow and energy intensive variotherm processes.

  13. Fluorinated Azobenzenes for Shape-Persistent Liquid Crystal Polymer Networks.

    PubMed

    Iamsaard, Supitchaya; Anger, Emmanuel; Aßhoff, Sarah Jane; Depauw, Alexis; Fletcher, Stephen P; Katsonis, Nathalie

    2016-08-16

    Liquid crystal polymer networks respond with an anisotropic deformation to a range of external stimuli. When doped with molecular photoswitches, these materials undergo complex shape modifications under illumination. As the deformations are reversed when irradiation stops, applications where the activated shape is required to have thermal stability have been precluded. Previous attempts to incorporate molecular switches into thermally stable photoisomers were unsuccessful at photogenerating macroscopic shapes that are retained over time. Herein, we show that to preserve photoactivated molecular deformation on the macroscopic scale, it is important not only to engineer the thermal stability of the photoswitch but also to adjust the cross-linking density in the polymer network and to optimize the molecular orientations in the material. Our strategy resulted in materials containing fluorinated azobenzenes that retain their photochemical shape for more than eight days, which constitutes the first demonstration of long-lived photomechanical deformation in liquid-crystal polymer networks.

  14. Swelling-induced surface instabilities in growing poroelastic polymer networks

    NASA Astrophysics Data System (ADS)

    Hennessy, Matthew G.; Vitale, Alessandra; Cabral, Joao T.; Matar, Omar K.

    2016-11-01

    The swelling that occurs when a deformable polymer network absorbs solvent can generate large compressive stresses which, in turn, can lead to a rich variety of surface instabilities. In this talk, we will discuss recent experiments by our group which suggest that the growth of a polymer network by photopolymerisation and the onset of swelling-induced surface instabilities can simultaneously occur and drive the self-assembly of complex three-dimensional structures. In addition, we will present a theoretical model of photopolymersation that captures the growth, swelling, and mechanical response of the polymer network. The model is based on an Eulerian formulation of nonlinear poroelasticity. The transport of monomer is described by a generalisation of Darcy's law that accounts for flow due to gradients in the pressure and composition. A combination of asymptotic analysis and finite-element simulations is used to explore the coupling between growth and instability as well as the resulting surface morphologies.

  15. Nonlinear dynamics and thermodynamics of azobenzene polymer networks

    NASA Astrophysics Data System (ADS)

    Oates, William S.; Bin, Jonghoon

    2013-04-01

    The nonlinear photomechanics and thermodynamics of azobenzene liquid crystal polymer networks is studied to quantify interactions between wavelength dependent molecular conformation changes that occur within a polymer network. The transfer of energy from light to liquid crystals to a polymer network strongly depends on the wavelength and polarization of light where trans or rod shaped azobenzene chromophores convert to a cis or kinked conformation and simultaneously may relax back to the trans state but in a different orientation. This behavior requires an understanding of the dynamic interactions between light and azobenzene molecules and thermodynamics of light-matter interactions. We investigate this behavior by quantifying transmission and absorption of electro-magnetic energy with stored energy within the solid material. This is conducted by introducing a set of optical order parameters coupled to photochemistry that evolve as a function of electro-magnetic radiation.

  16. Poly(Capro-Lactone) Networks as Actively Moving Polymers

    NASA Astrophysics Data System (ADS)

    Meng, Yuan

    Shape-memory polymers (SMPs), as a subset of actively moving polymers, form an exciting class of materials that can store and recover elastic deformation energy upon application of an external stimulus. Although engineering of SMPs nowadays has lead to robust materials that can memorize multiple temporary shapes, and can be triggered by various stimuli such as heat, light, moisture, or applied magnetic fields, further commercialization of SMPs is still constrained by the material's incapability to store large elastic energy, as well as its inherent one-way shape-change nature. This thesis develops a series of model semi-crystalline shape-memory networks that exhibit ultra-high energy storage capacity, with accurately tunable triggering temperature; by introducing a second competing network, or reconfiguring the existing network under strained state, configurational chain bias can be effectively locked-in, and give rise to two-way shape-actuators that, in the absence of an external load, elongates upon cooling and reversibly contracts upon heating. We found that well-defined network architecture plays essential role on strain-induced crystallization and on the performance of cold-drawn shape-memory polymers. Model networks with uniform molecular weight between crosslinks, and specified functionality of each net-point, results in tougher, more elastic materials with a high degree of crystallinity and outstanding shape-memory properties. The thermal behavior of the model networks can be finely modified by introducing non-crystalline small molecule linkers that effectively frustrates the crystallization of the network strands. This resulted in shape-memory networks that are ultra-sensitive to heat, as deformed materials can be efficiently triggered to revert to its permanent state upon only exposure to body temperature. We also coupled the same reaction adopted to create the model network with conventional free-radical polymerization to prepare a dual-cure "double

  17. Silsesquioxane nanoparticles with reactive internal functional groups

    NASA Astrophysics Data System (ADS)

    Brozek, Eric M.; Washton, Nancy M.; Mueller, Karl T.; Zharov, Ilya

    2017-02-01

    A series of silsesquioxane nanoparticles containing reactive internal organic functionalities throughout the entire particle body have been synthesized using a surfactant-free method with organosilanes as the sole precursors and a base catalyst. The organic functional groups incorporated are vinyl, allyl, mercapto, cyanoethyl, and cyanopropyl groups. The sizes and morphologies of the particles were characterized using SEM and nitrogen adsorption, while the compositions were confirmed using TGA, FT-IR, solid state NMR, and elemental analysis. The accessibility and reactivity of the functional groups inside the particles were demonstrated by performing bromination and reduction reactions in the interior of the particles.

  18. Network formation and gelation in telechelic star polymers.

    PubMed

    Wadgaonkar, Indrajit; Chatterji, Apratim

    2017-02-28

    We investigate the efficiency of gelation and network formation in telechelic star polymer melt, where the tips of polymer arms are dipoles while the rest of the monomers are uncharged. Our work is motivated by the experimental observations [A. Kulkarni et al., Macromolecules 48, 6580 (2015)] in which rheological studies of telechelic star polymers of poly-(L-lactide), a bio-degradable polymer, showed a drastic increase in elastic properties (up to 2000 times) compared to corresponding star polymers without the telechelic arm ends. In contrast to previous studies, we avoid using effective attractive Lennard-Jones potentials or dipolar potentials to model telechelic interactions. Instead we use explicit Coulomb positive and negative charges at the tip of polymer-arms of our bead-spring model of star polymers. By our simulations we show that the dipoles at the tip of star arms aggregate together to form clusters of dipoles. Each cluster has contributions from several stars, and in turn each star contributes to several clusters. Thus the entire polymer melt forms a connected network. Network forming tendencies decrease with a decrease of the value of the effective charge constituting the dipole: this can be experimentally realized by choosing a different ionomer for the star tip. We systematically varied the value of dipole charges, the fraction of star-arms with dipoles at the tip, and the length of the arms. The choice of explicit charges in our calculations enables us to make better quantitative predictions about the onset of gelation; moreover we get qualitatively distinct results about structural organization of dipoles within a dipole-cluster.

  19. Network formation and gelation in telechelic star polymers

    NASA Astrophysics Data System (ADS)

    Wadgaonkar, Indrajit; Chatterji, Apratim

    2017-02-01

    We investigate the efficiency of gelation and network formation in telechelic star polymer melt, where the tips of polymer arms are dipoles while the rest of the monomers are uncharged. Our work is motivated by the experimental observations [A. Kulkarni et al., Macromolecules 48, 6580 (2015)] in which rheological studies of telechelic star polymers of poly-(L-lactide), a bio-degradable polymer, showed a drastic increase in elastic properties (up to 2000 times) compared to corresponding star polymers without the telechelic arm ends. In contrast to previous studies, we avoid using effective attractive Lennard-Jones potentials or dipolar potentials to model telechelic interactions. Instead we use explicit Coulomb positive and negative charges at the tip of polymer-arms of our bead-spring model of star polymers. By our simulations we show that the dipoles at the tip of star arms aggregate together to form clusters of dipoles. Each cluster has contributions from several stars, and in turn each star contributes to several clusters. Thus the entire polymer melt forms a connected network. Network forming tendencies decrease with a decrease of the value of the effective charge constituting the dipole: this can be experimentally realized by choosing a different ionomer for the star tip. We systematically varied the value of dipole charges, the fraction of star-arms with dipoles at the tip, and the length of the arms. The choice of explicit charges in our calculations enables us to make better quantitative predictions about the onset of gelation; moreover we get qualitatively distinct results about structural organization of dipoles within a dipole-cluster.

  20. Advancing reversible shape memory by tuning the polymer network architecture

    SciTech Connect

    Li, Qiaoxi; Zhou, Jing; Vatankhah-Varnoosfaderani, Mohammad; Nykypanchuk, Dmytro; Gang, Oleg; Sheiko, Sergei S.

    2016-02-02

    Because of counteraction of a chemical network and a crystalline scaffold, semicrystalline polymer networks exhibit a peculiar behavior—reversible shape memory (RSM), which occurs naturally without applying any external force and particular structural design. There are three RSM properties: (i) range of reversible strain, (ii) rate of strain recovery, and (iii) decay of reversibility with time, which can be improved by tuning the architecture of the polymer network. Different types of poly(octylene adipate) networks were synthesized, allowing for control of cross-link density and network topology, including randomly cross-linked network by free-radical polymerization, thiol–ene clicked network with enhanced mesh uniformity, and loose network with deliberately incorporated dangling chains. It is shown that the RSM properties are controlled by average cross-link density and crystal size, whereas topology of a network greatly affects its extensibility. In conclusion, we have achieved 80% maximum reversible range, 15% minimal decrease in reversibility, and fast strain recovery rate up to 0.05 K–1, i.e., ca. 5% per 10 s at a cooling rate of 5 K/min.

  1. Advancing reversible shape memory by tuning the polymer network architecture

    DOE PAGES

    Li, Qiaoxi; Zhou, Jing; Vatankhah-Varnoosfaderani, Mohammad; ...

    2016-02-02

    Because of counteraction of a chemical network and a crystalline scaffold, semicrystalline polymer networks exhibit a peculiar behavior—reversible shape memory (RSM), which occurs naturally without applying any external force and particular structural design. There are three RSM properties: (i) range of reversible strain, (ii) rate of strain recovery, and (iii) decay of reversibility with time, which can be improved by tuning the architecture of the polymer network. Different types of poly(octylene adipate) networks were synthesized, allowing for control of cross-link density and network topology, including randomly cross-linked network by free-radical polymerization, thiol–ene clicked network with enhanced mesh uniformity, and loosemore » network with deliberately incorporated dangling chains. It is shown that the RSM properties are controlled by average cross-link density and crystal size, whereas topology of a network greatly affects its extensibility. In conclusion, we have achieved 80% maximum reversible range, 15% minimal decrease in reversibility, and fast strain recovery rate up to 0.05 K–1, i.e., ca. 5% per 10 s at a cooling rate of 5 K/min.« less

  2. Controlled architecture for improved macromolecular memory within polymer networks.

    PubMed

    DiPasquale, Stephen A; Byrne, Mark E

    2016-08-01

    This brief review analyzes recent developments in the field of living/controlled polymerization and the potential of this technique for creating imprinted polymers with highly structured architecture with macromolecular memory. As a result, it is possible to engineer polymers at the molecular level with increased homogeneity relating to enhanced template binding and transport. Only recently has living/controlled polymerization been exploited to decrease heterogeneity and substantially improve the efficiency of the imprinting process for both highly and weakly crosslinked imprinted polymers. Living polymerization can be utilized to create imprinted networks that are vastly more efficient than similar polymers produced using conventional free radical polymerization, and these improvements increase the role that macromolecular memory can play in the design and engineering of new drug delivery and sensing platforms.

  3. Competing dynamic phases of active polymer networks

    NASA Astrophysics Data System (ADS)

    Freedman, Simon; Banerjee, Shiladitya; Dinner, Aaron R.

    Recent experiments on in-vitro reconstituted assemblies of F-actin, myosin-II motors, and cross-linking proteins show that tuning local network properties can changes the fundamental biomechanical behavior of the system. For example, by varying cross-linker density and actin bundle rigidity, one can switch between contractile networks useful for reshaping cells, polarity sorted networks ideal for directed molecular transport, and frustrated networks with robust structural properties. To efficiently investigate the dynamic phases of actomyosin networks, we developed a coarse grained non-equilibrium molecular dynamics simulation of model semiflexible filaments, molecular motors, and cross-linkers with phenomenologically defined interactions. The simulation's accuracy was verified by benchmarking the mechanical properties of its individual components and collective behavior against experimental results at the molecular and network scales. By adjusting the model's parameters, we can reproduce the qualitative phases observed in experiment and predict the protein characteristics where phase crossovers could occur in collective network dynamics. Our model provides a framework for understanding cells' multiple uses of actomyosin networks and their applicability in materials research. Supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

  4. Experimental studies of siloxane polymers and their elastomeric networks

    SciTech Connect

    Kuo, Chung Mien

    1992-12-31

    Siloxane polymers have been investigated systematically for the purpose of a greater understanding of the structure-property relationships in terms of their synthesis, polymer blends and rubber elasticity of their crosslinked networks. This study includes a variety of topological structures: linear, cyclic and crosslinked networks of poly(dimethylsiloxane) (PDMS) and poly(dimethylco-methylphenylsiloxane) copolymers. Siloxane polymers with a narrow molecular weight distribution were prepared by a series of well-characterized organometallic polymerizations. The reaction conditions and mechanisms for preparing polyorganosiloxane chains and networks using organotin catalyst and promoters were discussed. Experimental evidence shows that formamide was one of the best additives to improve the reactivity of the tin dicarboxylate catalyst, which seems to suggest that the nucleophilic function of the additive was on the Sn atom. Since the PDMS and PMPS are immiscible under most conditions, the miscibility and phase behavior of siloxane blends were studied by a static light scattering t technique. THe influence of molar mass, the topological effect of cyclic and linear structures, the end-group effect, and the configurational isomerism effect on miscibility were examined. Silicon networks of PDMS, PMPS and their copolymers were prepared at room temperature using the crosslinked siloxane homopolymer and copolymer networks at equilibrium swelling in organic solvents and in liquid siloxane oligomers were investigated as function of crosslinking density and composition variation. The resulting interaction parameters for PDMS and PMPS from the swollen siloxane networks in siloxane oligomers individually were compared with those from measurements of the corresponding blend systems. Moreover, the stress-strain behavior of the siloxane polymer networks undergoing uniaxial deformation were evaluated by a stress-strain experiment.

  5. Controlling the electrical conductive network formation of polymer nanocomposites via polymer functionalization.

    PubMed

    Gao, Yangyang; Wu, Youping; Liu, Jun; Zhang, Liqun

    2016-12-06

    By adopting coarse-grained molecular dynamics simulations, the effect of polymer functionalization on the relationship between the microstructure and the electric percolation probability of nanorod filled polymer nanocomposites has been investigated. At a low chain functionalization degree, the nanorods in the polymer matrix form isolated aggregates with a local order structure. At a moderate chain functionalization degree, the local order structure of the nanorod aggregate is gradually broken up. Meanwhile, excessive functionalization chain beads can connect the isolated aggregates together, which leads to the maximum size of nanorod aggregation. At a high chain functionalization degree, it forms a single nanorod structure in the matrix. As a result, the highest percolation probability of the materials appears at the moderate chain functionalization degree, which is attributed to the formation of the tightly connected nanorod network by analyzing the main cluster. In addition, this optimum chain functionalization degree exists at two chain functionalization modes (random and diblock). Lastly, under the tensile field, even though the contact distance between nanorods nearly remains unchanged, the topological structure of the percolation network is broken down. While under the shear field, the contact distance between nanorods increases and the topological structure of the percolation network is broken down, which leads to a decrease in the percolation probability. In total, the topological structure of the percolation network dominates the percolation probability, which is not a necessary connection with the contact distance between nanorods. In summary, this work presents further understanding of the electric conductive properties of nanorod-filled nanocomposites with functionalized polymers.

  6. Polymer Solar Cells: Solubility Controls Fiber Network Formation.

    PubMed

    van Franeker, Jacobus J; Heintges, Gaël H L; Schaefer, Charley; Portale, Giuseppe; Li, Weiwei; Wienk, Martijn M; van der Schoot, Paul; Janssen, René A J

    2015-09-16

    The photoactive layer of polymer solar cells is commonly processed from a four-component solution, containing a semiconducting polymer and a fullerene derivative dissolved in a solvent-cosolvent mixture. The nanoscale dimensions of the polymer-fullerene morphology that is formed upon drying determines the solar cell performance, but the fundamental processes that govern the size of the phase-separated polymer and fullerene domains are poorly understood. Here, we investigate morphology formation of an alternating copolymer of diketopyrrolopyrrole and a thiophene-phenyl-thiophene oligomer (PDPPTPT) with relatively long 2-decyltetradecyl (DT) side chains blended with [6,6]-phenyl-C71-butyric acid methyl ester. During solvent evaporation the polymer crystallizes into a fibrous network. The typical width of these fibers is analyzed by quantification of transmission electron microscopic images, and is mainly determined by the solubility of the polymer in the cosolvent and the molecular weight of the polymer. A higher molecular weight corresponds to a lower solubility and film processing results in a smaller fiber width. Surprisingly, the fiber width is not related to the drying rate or the amount of cosolvent. We have made solar cells with fiber widths ranging from 28 to 68 nm and found an inverse relation between fiber width and photocurrent. Finally, by mixing two cosolvents, we develop a ternary solvent system to tune the fiber width. We propose a model based on nucleation-and-growth which can explain these measurements. Our results show that the width of the semicrystalline polymer fibers is not the result of a frozen dynamical state, but determined by the nucleation induced by the polymer solubility.

  7. Fluorinated Silsesquioxanes: Structure, Solubility, and Wetting (Briefing charts)

    DTIC Science & Technology

    2015-08-01

    Charts 3. DATES COVERED (From - To) July 2015-July 2015 4. TITLE AND SUBTITLE FLUORINATED SILSESQUIOXANES: STRUCTURE , SOLUBILITY, AND WETTING...FLUORINATED SILSESQUIOXANES: STRUCTURE , SOLUBILITY, AND WETTING Joseph Mabry, Andrew Guenthner, Scott Iacono, Raymond Campos, Sean Ramirez, Brian Moore...Fluorohexyl: Rf = -CH2CH2(CF2)3CF3 Fluoropropyl: Rf = -CH2CH2CF3 Linear disiloxane resin (M2) Structure of candidate molecules ACS AMI, 2010 15DISTRIBUTION

  8. Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

    NASA Astrophysics Data System (ADS)

    Rosenthal-Kim, Emily Quinn

    The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight

  9. Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization.

    PubMed

    Xing, Yuxiu; Peng, Jun; Xu, Kai; Lin, Weihong; Gao, Shuxi; Ren, Yuanyuan; Gui, Xuefeng; Liang, Shengyuan; Chen, Mingcai

    2016-02-01

    We prepared core-shell polymer-silsesquioxane hybrid microcapsules from cage-like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core-shell latex particles were achieved. The polymer latex particles were subsequently transformed into well-defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High-resolution TEM and nitrogen adsorption-desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2-3 nm. The nanospheres exhibited large surface areas (up to 486 m(2)  g(-1) ) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g(-1) ). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one-step template-free method for various applications.

  10. Thermoelectric behavior of segregated-network polymer nanocomposites.

    PubMed

    Yu, Choongho; Kim, Yeon Seek; Kim, Dasaroyong; Grunlan, Jaime C

    2008-12-01

    Segregated-network carbon nanotube (CNT)-polymer composites were prepared, and their thermoelectric properties were measured as a function of CNT concentration at room temperature. This study shows that electrical conductivity can be dramatically increased by creating a network of CNTs in the composite, while the thermal conductivity and thermopower remain relatively insensitive to the filler concentration. This behavior results from thermally disconnected, but electrically connected, junctions in the nanotube network, which makes it feasible to tune the properties in favor of a higher thermoelectric figure of merit. With a CNT concentration of 20 wt %, these composites exhibit an electrical conductivity of 4800 S/m, thermal conductivity of 0.34 W/m x K and a thermoelectric figure of merit (ZT) greater than 0.006 at room temperature. This study suggests that polymeric thermoelectrics are possible and provides the basis for further development of lightweight, low-cost, and nontoxic polymer composites for thermoelectric applications in the future.

  11. Computer-Aided Design of Photocured Polymer Networks

    NASA Astrophysics Data System (ADS)

    Sarkar, Swarnavo; Lin-Gibson, Sheng; Chiang, Martin

    Light-initiated free radical polymerization is widely used for manufacturing biomaterials, scaffolds for micomolding, and is being developed as a method for fast 3D fabrication. This process has a large set of control parameters in the composition of the photocurable matrix and the photocuring conditions. But a quantitative map between the choice of parameters and the properties of the resultant polymer is currently unavailable. We present a computational approach to simulate the growth of a polymer network using the stochastic differential equations of reactions and diffusion for a photocuring system. This method allows us to sample trajectories of a growing polymer network in silico. Thus, we provide a computational alternative to synthesize and probe a polymer network for properties like the degree of conversion, structure factor, density of states, and viscosity. We present simulation results that agree with the universal features observed in photopolymerization. Our proposed method enables a thorough and systematic search over the entire parameter space to discover interesting combinations for synthesis.

  12. High-Performance, Semi-Interpenetrating Polymer Network

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H.; Lowther, Sharon E.; Smith, Janice Y.; Cannon, Michelle S.; Whitehead, Fred M.; Ely, Robert M.

    1992-01-01

    High-performance polymer made by new synthesis in which one or more easy-to-process, but brittle, thermosetting polyimides combined with one or more tough, but difficult-to-process, linear thermoplastics to yield semi-interpenetrating polymer network (semi-IPN) having combination of easy processability and high tolerance to damage. Two commercially available resins combined to form tough, semi-IPN called "LaRC-RP49." Displays improvements in toughness and resistance to microcracking. LaRC-RP49 has potential as high-temperature matrix resin, adhesive, and molding resin. Useful in aerospace, automotive, and electronic industries.

  13. Design and Application of Nanogel-Based Polymer Networks

    NASA Astrophysics Data System (ADS)

    Dailing, Eric Alan

    Crosslinked polymer networks have wide application in biomaterials, from soft hydrogel scaffolds for cell culture and tissue engineering to glassy, high modulus dental restoratives. Composite materials formed with nanogels as a means for tuning network structure on the nanoscale have been reported, but no investigation into nanogels as the primary network component has been explored to this point. This thesis was dedicated to studying network formation from the direct polymerization of nanogels and investigating applications for these unique materials. Covalently crosslinked polymer networks were synthesized from polymerizable nanogels without the use of reactive small monomers or oligomers. Network properties were controlled by the chemical and physical properties of the nanogel, allowing for materials to be designed from nanostructured macromolecular precursors. Nanogels were synthesized from a thermally initiated solution free radical polymerization of a monomethacrylate, a dimethacrylate, and a thiol-based chain transfer agent. Monomers with a range of hydrophilic and hydrophobic character were copolymerized, and polymerizable groups were introduced through an alcohol-isocyanate click reaction. Nanogels were dispersible in water up to 75 wt%, including nanogels that contained a relatively high fraction of a conventionally water-insoluble component. Nanogels with molecular weights that ranged from 10's to 100's of kDa and hydrodynamic radii between 4 and 10 nm were obtained. Macroscopic crosslinked polymer networks were synthesized from the photopolymerization of methacrylate-functionalized nanogels in inert solvent, which was typically water. The nanogel composition and internal branching density affected both covalent and non-covalent interparticle interactions, which dictated the final mechanical properties of the networks. Nanogels with progressively disparate hydrophilic and hydrophobic character were synthesized to explore the potential for creating

  14. Thermosetting Poly(imide silsesquioxane)s Featuring Reduced Moisture Affinity and Improved Processability (Post-print)

    DTIC Science & Technology

    2013-09-11

    Journal Article 3. DATES COVERED (From - To) August 2013- October 2013 4. TITLE AND SUBTITLE Thermosetting Poly(imide silsesquioxane)s Featuring Reduced... Journal article published in the ACS Macromolecules Vol. #46, Issue #18 September 2013. PA Case Number: #13496; Clearance Date: 10 Oct 2013...from oligoamic acid to oligoimide is attributed to a lower degree of rotational freedom and thus more chemical environments. Rheology . Figure 5

  15. Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

    PubMed

    Cheng, Chih-Chia; Chuang, Wei-Tsung; Lee, Duu-Jong; Xin, Zhong; Chiu, Chih-Wei

    2017-03-01

    A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization.

  16. Fracture energy of polymer gels with controlled network structures

    NASA Astrophysics Data System (ADS)

    Akagi, Yuki; Sakurai, Hayato; Gong, Jian Ping; Chung, Ung-il; Sakai, Takamasa

    2013-10-01

    We have investigated the fracture behaviors of tetra-arm polyethylene glycol (Tetra-PEG) gels with controlled network structures. Tetra-PEG gels were prepared by AB-type crosslink-coupling of mutually reactive tetra-arm prepolymers with different concentrations and molecular weights. This series of controlled network structures, for the first time, enabled us to quantitatively examine the Lake-Thomas model, which is the most popular model predicting fracture energies of elastomers. The experimental data showed good agreement with the Lake-Thomas model, and indicated a new molecular interpretation for the displacement length (L), the area around a crack tip within which the network strands are fully stretched. L corresponded to the three times of end-to-end distance of network strands, regardless of all parameters examined. We conclude that the Lake-Thomas model can quantitatively predict the fracture energy of polymer network without trapped entanglements, with the enhancement factor being near 3.

  17. Fracture energy of polymer gels with controlled network structures.

    PubMed

    Akagi, Yuki; Sakurai, Hayato; Gong, Jian Ping; Chung, Ung-il; Sakai, Takamasa

    2013-10-14

    We have investigated the fracture behaviors of tetra-arm polyethylene glycol (Tetra-PEG) gels with controlled network structures. Tetra-PEG gels were prepared by AB-type crosslink-coupling of mutually reactive tetra-arm prepolymers with different concentrations and molecular weights. This series of controlled network structures, for the first time, enabled us to quantitatively examine the Lake-Thomas model, which is the most popular model predicting fracture energies of elastomers. The experimental data showed good agreement with the Lake-Thomas model, and indicated a new molecular interpretation for the displacement length (L), the area around a crack tip within which the network strands are fully stretched. L corresponded to the three times of end-to-end distance of network strands, regardless of all parameters examined. We conclude that the Lake-Thomas model can quantitatively predict the fracture energy of polymer network without trapped entanglements, with the enhancement factor being near 3.

  18. Investigation on the vibrational and structural properties of a self-structured bridged silsesquioxane.

    PubMed

    Creff, Gaëlle; Arrachart, Guilhem; Hermet, Patrick; Wadepohl, Hubert; Almairac, Robert; Maurin, David; Sauvajol, Jean-Louis; Carcel, Carole; Moreau, Joël J E; Dieudonné, Philippe; Man, Michel Wong Chi; Bantignies, Jean-Louis

    2012-04-28

    The crystalline structure of ureidopyrimidinone-based silane (UPY) has been determined. The local and long range order structuring of the bridged silsesquioxane (MUPY) resulting from the sol-gel hydrolysis-condensation of the former precursor has been investigated by MFTIR (Mid Fourier Transform InfraRed) combined with DFT (Density Functional Theory) and XRD (X-ray diffraction) studies. These studies showed that a long range structuring exists within the organic fragments with the transcription of the DDAA (Donor-Donor-Acceptor-Acceptor) H-bonding array from UPY to MUPY whereas a disordered siloxane network was revealed in the hybrid material.

  19. Photo-induced Mass Transport through Polymer Networks

    NASA Astrophysics Data System (ADS)

    Meng, Yuan; Anthamatten, Mitchell

    2014-03-01

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

  20. An easily fabricated high performance ionic polymer based sensor network

    NASA Astrophysics Data System (ADS)

    Zhu, Zicai; Wang, Yanjie; Hu, Xiaopin; Sun, Xiaofei; Chang, Longfei; Lu, Pin

    2016-08-01

    Ionic polymer materials can generate an electrical potential from ion migration under an external force. For traditional ionic polymer metal composite sensors, the output voltage is very small (a few millivolts), and the fabrication process is complex and time-consuming. This letter presents an ionic polymer based network of pressure sensors which is easily and quickly constructed, and which can generate high voltage. A 3 × 3 sensor array was prepared by casting Nafion solution directly over copper wires. Under applied pressure, two different levels of voltage response were observed among the nine nodes in the array. For the group producing the higher level, peak voltages reached as high as 25 mV. Computational stress analysis revealed the physical origin of the different responses. High voltages resulting from the stress concentration and asymmetric structure can be further utilized to modify subsequent designs to improve the performance of similar sensors.

  1. Shape memory polymer network with thermally distinct elasticity and plasticity

    PubMed Central

    Zhao, Qian; Zou, Weike; Luo, Yingwu; Xie, Tao

    2016-01-01

    Stimuli-responsive materials with sophisticated yet controllable shape-changing behaviors are highly desirable for real-world device applications. Among various shape-changing materials, the elastic nature of shape memory polymers allows fixation of temporary shapes that can recover on demand, whereas polymers with exchangeable bonds can undergo permanent shape change via plasticity. We integrate the elasticity and plasticity into a single polymer network. Rational molecular design allows these two opposite behaviors to be realized at different temperature ranges without any overlap. By exploring the cumulative nature of the plasticity, we demonstrate easy manipulation of highly complex shapes that is otherwise extremely challenging. The dynamic shape-changing behavior paves a new way for fabricating geometrically complex multifunctional devices. PMID:26824077

  2. Constitutive equation for polymer networks with phonon fluctuations.

    PubMed

    Hansen, Rasmus; Skov, Anne Ladegaard; Hassager, Ole

    2008-01-01

    Recent research by Xing [Phys. Rev. Lett. 98, 075502 (2007)] has provided an expression for the Helmholtz free energy related to phonon fluctuations in polymer networks. We extend this result by constructing the corresponding nonlinear constitutive equation, usable for entirely general, volume conserving deformation fields. Constitutive equations for the sliplink model and the tube model are derived and the three models are examined by comparison with each other and with data from Xu and Mark [Rubber Chem. Technol. 63, 276 (1990)] and Wang and Mark [J. Polym. Sci., Part B: Polym. Phys. 30, 801 (1992)]. Elastic moduli are derived for the three models and compared with the moduli determined from the chemical stoichiometry. We conclude that the sliplink model and the phonon fluctuation model are relatively consistent with each other and with the data. The tube model seems consistent neither with the other models nor with the data.

  3. Dirac Cones in two-dimensional conjugated polymer networks

    NASA Astrophysics Data System (ADS)

    Adjizian, Jean-Joseph; Briddon, Patrick; Humbert, Bernard; Duvail, Jean-Luc; Wagner, Philipp; Adda, Coline; Ewels, Christopher

    2014-12-01

    Linear electronic band dispersion and the associated Dirac physics has to date been limited to special-case materials, notably graphene and the surfaces of three-dimensional (3D) topological insulators. Here we report that it is possible to create two-dimensional fully conjugated polymer networks with corresponding conical valence and conduction bands and linear energy dispersion at the Fermi level. This is possible for a wide range of polymer types and connectors, resulting in a versatile new family of experimentally realisable materials with unique tuneable electronic properties. We demonstrate their stability on substrates and possibilities for doping and Dirac cone distortion. Notably, the cones can be maintained in 3D-layered crystals. Resembling covalent organic frameworks, these materials represent a potentially exciting new field combining the unique Dirac physics of graphene with the structural flexibility and design opportunities of organic-conjugated polymer chemistry.

  4. Multiple relaxation modes in associative polymer networks with varying connectivity

    NASA Astrophysics Data System (ADS)

    Bohdan, M.; Sprakel, J.; van der Gucht, J.

    2016-09-01

    The dynamics and mechanics of networks depend sensitively on their spatial connectivity. To explore the effect of connectivity on local network dynamics, we prepare transient polymer networks in which we systematically cut connecting bonds. We do this by creating networks formed from hydrophobically modified difunctionalized polyethylene glycol chains. These form physical gels, consisting of flowerlike micelles that are transiently cross-linked by connecting bridges. By introducing monofunctionalized chains, we can systematically reduce the number of bonds between micelles and thus lower the network connectivity, which strongly reduces the network elasticity and relaxation time. Dynamic light scattering reveals a complex relaxation dynamics that are not apparent in bulk rheology. We observe three distinct relaxation modes. First we find a fast diffusive mode that does not depend on the number of bridges and is attributed to the diffusion of micelles within a cage formed by neighboring micelles. A second, intermediate mode depends strongly on network connectivity but surprisingly is independent of the scattering vector q . We attribute this viscoelastic mode to fluctuations in local connectivity of the network. The third, slowest mode is also diffusive and is attributed to the diffusion of micelle clusters through the viscoelastic matrix. These results shed light on the microscopic dynamics in weakly interconnected transient networks.

  5. Shape memory polymers based on uniform aliphatic urethane networks

    SciTech Connect

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  6. Reconfigurable Polymer Networks for Improved Treatment of Intracranial Aneurysms

    NASA Astrophysics Data System (ADS)

    Ninh, Chi Suze Q.

    Endovascular embolization of intracranial aneurysms is a minimally invasive treatment in which an implanted material forms a clot to isolate the weakened vessel. Current strategy suffers from long-term potential failure modes. These potential failure modes include (1) enzymatic degradation of the fibrin clot that leads to compaction of the embolic agent, (2) incomplete filling of the aneurysm sac by embolic agent, and (3) challenging geometry of wide neck aneurysms. In the case of wide neck aneurysms, usually an assisting metal stent is used to help open the artery. However, metal stents with much higher modulus in comparison to the soft blood vessel can cause biocompatibilities issues in the long term such as infection and scarring. Motivated to solve these challenges associated with endovascular embolization, strategies to synthesize and engineer reconfigurable and biodegradable polymers as alternative therapies are evaluated in this thesis. (1) Reconfiguration of fibrin gel's modulus was achieved through crosslinking with genipin released from a biodegradable polymer matrix. (2) Reconfigurability can also be achieved by transforming triblock co-polymer hydrogel into photoresponsive material through incorporation of melanin nanoparticles as efficient photosensitizers. (3) Finally, reconfigurability can be conferred on biodegradable polyester networks via Diels-Alder coupling of furan pendant groups and dimaleimide crosslinking agent. Taken all together, this thesis describes strategies to transform a broad class of polymer networks into reconfigurable materials for improved treatment of intracranial aneurysms as well as for other biomedical applications.

  7. Flash freezing route to mesoporous polymer nanofibre networks

    PubMed Central

    Samitsu, Sadaki; Zhang, Rui; Peng, Xinsheng; Krishnan, Mohan Raj; Fujii, Yoshihisa; Ichinose, Izumi

    2013-01-01

    There are increasing requirements worldwide for advanced separation materials with applications in environmental protection processes. Various mesoporous polymeric materials have been developed and they are considered as potential candidates. It is still challenging, however, to develop economically viable and durable separation materials from low-cost, mass-produced materials. Here we report the fabrication of a nanofibrous network structure from common polymers, based on a microphase separation technique from frozen polymer solutions. The resulting polymer nanofibre networks exhibit large free surface areas, exceeding 300 m2 g−1, as well as small pore radii as low as 1.9 nm. These mesoporous polymer materials are able to rapidly adsorb and desorb a large amount of carbon dioxide and are also capable of condensing organic vapours. Furthermore, the nanofibres made of engineering plastics with high glass transition temperatures over 200 °C exhibit surprisingly high, temperature-dependent adsorption of organic solvents from aqueous solution. PMID:24145702

  8. Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis, Assembly, and Applications.

    PubMed

    Ye, Qun; Zhou, Hui; Xu, Jianwei

    2016-05-06

    Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high-temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono-functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS-based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS-based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.

  9. A computational molecular design framework for crosslinked polymer networks

    PubMed Central

    Eslick, J.C.; Ye, Q.; Park, J.; Topp, E.M.; Spencer, P.; Camarda, K.V.

    2013-01-01

    Crosslinked polymers are important in a very wide range of applications including dental restorative materials. However, currently used polymeric materials experience limited durability in the clinical oral environment. Researchers in the dental polymer field have generally used a time-consuming experimental trial-and-error approach to the design of new materials. The application of computational molecular design (CMD) to crosslinked polymer networks has the potential to facilitate development of improved polymethacrylate dental materials. CMD uses quantitative structure property relations (QSPRs) and optimization techniques to design molecules possessing desired properties. This paper describes a mathematical framework which provides tools necessary for the application of CMD to crosslinked polymer systems. The novel parts of the system include the data structures used, which allow for simple calculation of structural descriptors, and the formulation of the optimization problem. A heuristic optimization method, Tabu Search, is used to determine candidate monomers. Use of a heuristic optimization algorithm makes the system more independent of the types of QSPRs used, and more efficient when applied to combinatorial problems. A software package has been created which provides polymer researchers access to the design framework. A complete example of the methodology is provided for polymethacrylate dental materials. PMID:23904665

  10. Interpenetrating Polymer Networks as Innovative Drug Delivery Systems

    PubMed Central

    Lohani, Alka; Singh, Garima; Bhattacharya, Shiv Sankar; Verma, Anurag

    2014-01-01

    Polymers have always been valuable excipients in conventional dosage forms, also have shown excellent performance into the parenteral arena, and are now capable of offering advanced and sophisticated functions such as controlled drug release and drug targeting. Advances in polymer science have led to the development of several novel drug delivery systems. Interpenetrating polymer networks (IPNs) have shown superior performances over the conventional individual polymers and, consequently, the ranges of applications have grown rapidly for such class of materials. The advanced properties of IPNs like swelling capacity, stability, biocompatibility, nontoxicity and biodegradability have attracted considerable attention in pharmaceutical field especially in delivering bioactive molecules to the target site. In the past few years various research reports on the IPN based delivery systems showed that these carriers have emerged as a novel carrier in controlled drug delivery. The present review encompasses IPNs, their types, method of synthesis, factors which affects the morphology of IPNs, extensively studied IPN based drug delivery systems, and some natural polymers widely used for IPNs. PMID:24949205

  11. Microstructure and rheology of microfibril-polymer networks.

    PubMed

    Veen, Sandra J; Versluis, Peter; Kuijk, Anke; Velikov, Krassimir P

    2015-12-14

    By using an adsorbing polymer in combination with mechanical de-agglomeration, the microstructure and rheological properties of networks of microfibrils could be controlled. By the addition of sodium carboxymethyl cellulose during de-agglomeration of networks of bacterial cellulose, the microstructure could be changed from an inhomogeneous network with bundles of microfibrils and voids to a more homogeneous spread and alignment of the particles. As a result the macroscopic rheological properties were altered. Although still elastic and gel-like in nature, the elasticity and viscous behavior of the network as a function of microfibril concentration is altered. The microstructure is thus changed by changing the surface properties of the building blocks leading to a direct influence on the materials macroscopic behavior.

  12. Semi-interpenetrating polymer network for tougher and more microcracking resistant high temperature polymers

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H. (Inventor)

    1992-01-01

    This invention is a semi-interpenetrating polymer network which includes a high performance thermosetting polyimide having a nadic end group acting as a crosslinking site and a high performance linear thermoplastic polyimide. An improved high temperature matrix resin is provided which is capable of performing at 316 C in air for several hundreds of hours. This resin has significantly improved toughness and microcracking resistance, excellent processability and mechanical performance, and cost effectiveness.

  13. Primitive chain network simulations for asymmetric star polymers

    NASA Astrophysics Data System (ADS)

    Masubuchi, Yuichi; Yaoita, Takatoshi; Matsumiya, Yumi; Watanabe, Hiroshi

    2011-05-01

    For branched polymers, the curvilinear motion of the branch point along the backbone is a significant relaxation source but details of this motion have not been well understood. This study conducts multi-chain sliplink simulations to examine effects of the spatial fluctuation and curvilinear hopping of the branch point on the viscoelastic relaxation. The simulation is based on the primitive chain network model that allows the spatial fluctuations of sliplink and branch point and the chain sliding along the backbone according to the subchain tension, chemical potential gradients, drag force against medium, and random force. The sliplinks are created and/or disrupted through the motion of chain ends. The curvilinear hopping of the branch point along the backbone is allowed to occur when all sliplinks on a branched arm are lost. The simulations considering the fluctuation and the hopping of the branch point described well the viscoelastic data for symmetric and asymmetric star polymers with a parameter set common to the linear polymer. On the other hand, the simulations without the branch point motion predicted unreasonably slow relaxation for asymmetric star polymers. For asymmetric star polymers, further tests with and without the branch point hopping revealed that the hopping is much less important compared to the branch point fluctuation when the lengths of the short and long backbone arms are not very different and the waiting time for the branch point hopping (time for removal of all sliplinks on the short arm) is larger than the backbone relaxation time. Although this waiting time changes with the hopping condition, the above results suggest a significance of the branch point fluctuation in the actual relaxation of branch polymers.

  14. Progress in the development of interpenetrating polymer network hydrogels.

    PubMed

    Myung, David; Waters, Dale; Wiseman, Meredith; Duhamel, Pierre-Emile; Noolandi, Jaan; Ta, Christopher N; Frank, Curtis W

    2008-04-28

    Interpenetrating polymer networks (IPNs) have been the subject of extensive study since their advent in the 1960s. Hydrogel IPN systems have garnered significant attention in the last two decades due to their usefulness in biomedical applications. Of particular interest are the mechanical enhancements observed in "double network" IPN systems which exhibit nonlinear increases in fracture properties despite being composed of otherwise weak polymers. We have built upon pioneering work in this field as well as in responsive IPN systems to develop an IPN system based on end-linked poly-(ethylene glycol) (PEG) and loosely crosslinked poly(acrylic acid) (PAA) with hydrogen bond-reinforced strain-hardening behavior in water and high initial Young's moduli under physiologic buffer conditions through osmotically induced pre-stress. Uniaxial tensile tests and equilibrium swelling measurements were used to study PEG/PAA IPN hydrogels having second networks prepared with varying crosslinking and photoinitiator content, pH, solids content, and comonomers. Studies involving the addition of non-ionic comonomers and neutralization of the second network showed that template polymerization appears to be important in the formation of mechanically enhanced IPNs.

  15. Electropolymerization on wireless electrodes towards conducting polymer microfibre networks

    PubMed Central

    Koizumi, Yuki; Shida, Naoki; Ohira, Masato; Nishiyama, Hiroki; Tomita, Ikuyoshi; Inagi, Shinsuke

    2016-01-01

    Conducting polymers can be easily obtained by electrochemical oxidation of aromatic monomers on an electrode surface as a film state. To prepare conducting polymer fibres by electropolymerization, templates such as porous membranes are necessary in the conventional methods. Here we report the electropolymerization of 3,4-ethylenedioxythiophene and its derivatives by alternating current (AC)-bipolar electrolysis. Poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives were found to propagate as a fibre form from the ends of Au wires used as bipolar electrodes (BPEs) parallel to an external electric field, without the use of templates. The effects of applied frequency and of the solvent on the morphology, growth rate and degree of branching of these PEDOT fibres were investigated. In addition, a chain-growth model for the formation of conductive material networks was also demonstrated. PMID:26804140

  16. Electropolymerization on wireless electrodes towards conducting polymer microfibre networks

    NASA Astrophysics Data System (ADS)

    Koizumi, Yuki; Shida, Naoki; Ohira, Masato; Nishiyama, Hiroki; Tomita, Ikuyoshi; Inagi, Shinsuke

    2016-01-01

    Conducting polymers can be easily obtained by electrochemical oxidation of aromatic monomers on an electrode surface as a film state. To prepare conducting polymer fibres by electropolymerization, templates such as porous membranes are necessary in the conventional methods. Here we report the electropolymerization of 3,4-ethylenedioxythiophene and its derivatives by alternating current (AC)-bipolar electrolysis. Poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives were found to propagate as a fibre form from the ends of Au wires used as bipolar electrodes (BPEs) parallel to an external electric field, without the use of templates. The effects of applied frequency and of the solvent on the morphology, growth rate and degree of branching of these PEDOT fibres were investigated. In addition, a chain-growth model for the formation of conductive material networks was also demonstrated.

  17. Tough, processable semi-interpenetrating polymer networks from monomer reactants

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H. (Inventor)

    1994-01-01

    A high temperature semi-interpenetrating polymer network (semi-IPN) was developed which had significantly improved processability, damage tolerance, and mechanical performance, when compared to the commercial Thermid materials. This simultaneous semi-IPN was prepared by mixing the monomer precursors of Thermid AL-600 (a thermoset) and NR-150B2 (a thermoplastic) and allowing the monomers to react randomly upon heating. This reaction occurs at a rate which decreases the flow and broadens the processing window. Upon heating at a higher temperature, there is an increase in flow. Because of the improved flow properties, broadened processing window and enhanced toughness, high strength polymer matrix composites, adhesives and molded articles can now be prepared from the acetylene end-capped polyimides which were previously inherently brittle and difficult to process.

  18. Surprising high hydrophobicity of polymer networks from hydrophilic components.

    PubMed

    Attanasio, Agnese; Bayer, Ilker S; Ruffilli, Roberta; Ayadi, Farouk; Athanassiou, Athanassia

    2013-06-26

    We report a simple and inexpensive method of fabricating highly hydrophobic novel materials based on interpenetrating networks of polyamide and poly(ethyl cyanoacrylate) hydrophilic components. The process is a single-step solution casting from a common solvent, formic acid, of polyamide and ethyl cyanoacrylate monomers. After casting and subsequent solvent evaporation, the in situ polymerization of ethyl cyanoacrylate monomer forms polyamide-poly(ethyl cyanoacrylate) interpenetrating network films. The interpenetrating networks demonstrate remarkable waterproof properties allowing wettability control by modulating the concentration of the components. In contrast, pure polyamide and poly(ethyl cyanoacrylate) films obtained from formic acid solutions are highly hygroscopic and hydrophilic, respectively. The polymerization of ethyl cyanoacrylate in the presence of polyamide promotes molecular interactions between the components, which reduce the available hydrophilic moieties and render the final material hydrophobic. The wettability, morphology, and thermo-physical properties of the polymeric coatings were characterized. The materials developed in this work take advantage of the properties of both polymers in a single blend and above all, due to their hydrophobic nature and minimal water uptake, can extend the application range of the individual polymers where water repellency is required.

  19. Incompletely-Condensed Fluorinated Silsesquioxane: Synthesis and Crystal Structure

    DTIC Science & Technology

    2011-11-29

    other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a ...ABSTRACT A recently developed sub-class of POSS, fluorinated polyhedral oligomeric silsesquioxane (F-POSS), consists of a Si-O core with a periphery of...incompletely-condensed silsesquioxane, (CF3(CF2)7CH2CH2)8Si8O11(OH)2, has been synthesized via a multi-step synthesis (52% yield). The structure was

  20. Self-Healing of Polymer Networks with Reversible Bonds

    NASA Astrophysics Data System (ADS)

    Rubinstein, Michael

    2015-03-01

    Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess nonequilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. The model is extended to describe enhanced toughness of dual networks with both permanent and reversible cross-links. This work was done in collaboration with Drs. Ludwik Leibler, Li-Heng Cai, Evgeny B. Stukalin, N. Arun Kumar and supported by the National Science Foundation.

  1. Strain hardening in polymer glasses: limitations of network models.

    PubMed

    Hoy, Robert S; Robbins, Mark O

    2007-09-14

    Simulations are used to examine the microscopic origins of strain hardening in polymer glasses. While traditional entropic network models can be fit to the total stress, their underlying assumptions are inconsistent with simulation results. There is a substantial energetic contribution to the stress that rises rapidly as segments between entanglements are pulled taut. The thermal component of stress is less sensitive to entanglements, mostly irreversible, and directly related to the rate of local plastic rearrangements. Entangled and unentangled chains show the same strain hardening when plotted against the microscopic chain orientation rather than the macroscopic strain.

  2. Strain Hardening in Polymer Glasses: Limitations of Network Models

    NASA Astrophysics Data System (ADS)

    Hoy, Robert S.; Robbins, Mark O.

    2007-09-01

    Simulations are used to examine the microscopic origins of strain hardening in polymer glasses. While traditional entropic network models can be fit to the total stress, their underlying assumptions are inconsistent with simulation results. There is a substantial energetic contribution to the stress that rises rapidly as segments between entanglements are pulled taut. The thermal component of stress is less sensitive to entanglements, mostly irreversible, and directly related to the rate of local plastic rearrangements. Entangled and unentangled chains show the same strain hardening when plotted against the microscopic chain orientation rather than the macroscopic strain.

  3. Interpenetrating polymer network ion exchange membranes and method for preparing same

    DOEpatents

    Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

    1989-01-01

    Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

  4. Modular and orthogonal synthesis of hybrid polymers and networks.

    PubMed

    Liu, Shuang; Dicker, Kevin T; Jia, Xinqiao

    2015-03-28

    Biomaterials scientists strive to develop polymeric materials with distinct chemical make-up, complex molecular architectures, robust mechanical properties and defined biological functions by drawing inspirations from biological systems. Salient features of biological designs include (1) repetitive presentation of basic motifs; and (2) efficient integration of diverse building blocks. Thus, an appealing approach to biomaterials synthesis is to combine synthetic and natural building blocks in a modular fashion employing novel chemical methods. Over the past decade, orthogonal chemistries have become powerful enabling tools for the modular synthesis of advanced biomaterials. These reactions require building blocks with complementary functionalities, occur under mild conditions in the presence of biological molecules and living cells and proceed with high yield and exceptional selectivity. These chemistries have facilitated the construction of complex polymers and networks in a step-growth fashion, allowing facile modulation of materials properties by simple variations of the building blocks. In this review, we first summarize features of several types of orthogonal chemistries. We then discuss recent progress in the synthesis of step growth linear polymers, dendrimers and networks that find application in drug delivery, 3D cell culture and tissue engineering. Overall, orthogonal reactions and modulular synthesis have not only minimized the steps needed for the desired chemical transformations but also maximized the diversity and functionality of the final products. The modular nature of the design, combined with the potential synergistic effect of the hybrid system, will likely result in novel hydrogel matrices with robust structures and defined functions.

  5. Cascade synthesis of a gold nanoparticle–network polymer composite

    DOE PAGES

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

    2015-11-02

    In this paper, the multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate endderivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4]-, formation of large aggregated Au NPs andmore » oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multilamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Finally, optical spectroscopy shows a notable red shift (Δλ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.« less

  6. Cascade synthesis of a gold nanoparticle-network polymer composite

    DOE PAGES

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

    2015-11-02

    In this paper, the multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate endderivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4]-, formation of large aggregated Au NPs andmore » oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multilamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Finally, optical spectroscopy shows a notable red shift (Δλ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.« less

  7. Modular and Orthogonal Synthesis of Hybrid Polymers and Networks

    PubMed Central

    Liu, Shuang; Dicker, Kevin T.; Jia, Xinqiao

    2015-01-01

    Biomaterials scientists strive to develop polymeric materials with distinct chemical make-up, complex molecular architectures, robust mechanical properties and defined biological functions by drawing inspirations from biological systems. Salient features of biological designs include (1) repetitive presentation of basic motifs; and (2) efficient integration of diverse building blocks. Thus, an appealing approach to biomaterials synthesis is to combine synthetic and natural building blocks in a modular fashion employing novel chemical methods. Over the past decade, orthogonal chemistries have become powerful enabling tools for the modular synthesis of advanced biomaterials. These reactions require building blocks with complementary functionalities, occur under mild conditions in the presence of biological molecules and living cells and proceed with high yield and exceptional selectivity. These chemistries have facilitated the construction of complex polymers and networks in a step-growth fashion, allowing facile modulation of materials properties by simple variations of the building blocks. In this review, we first summarize features of several types of orthogonal chemistries. We then discuss recent progress in the synthesis of step growth linear polymers, dendrimers and networks that find application in drug delivery, 3D cell culture and tissue engineering. Overall, orthogonal reactions and modulular synthesis have not only minimized the steps needed for the desired chemical transformations but also maximized the diversity and functionality of the final products. The modular nature of the design, combined with the potential synergistic effect of the hybrid system, will likely result in novel hydrogel matrices with robust structures and defined functions. PMID:25572255

  8. Characterization of a polymer-infiltrated ceramic-network material

    PubMed Central

    Corazza, Pedro H.; Zhang, Yu

    2015-01-01

    Objectives To characterize the microstructure and determine some mechanical properties of a polymer-ingfiltrated ceramic-network (PICN) material (Vita Enamic, Vita Zahnfabrik) available for CAD–CAM systems. Methods Specimens were fabricated to perform quantitative and qualitative analyses of the material’s microstructure and to determine the fracture toughness (KIc), density (ρ), Poisson’s ratio (v) and Young’s modulus (E). KIc was determined using V-notched specimens and the short beam toughness method, where bar-shaped specimens were notched and 3-point loaded to fracture. ρ was calculated using Archimedes principle, and v and E were measured using an ultrasonic thickness gauge with a combination of a pulse generator and an oscilloscope. Results Microstructural analyses showed a ceramic- and a polymer-based interpenetrating network. Mean and standard deviation values for the properties evaluated were: KIc = 1.09 ± 0.05 MPa m1/2, ρ = 2.09 ± 0.01 g/cm3, v = 0.23 ± 0.002 and E = 37.95 ± 0.34 GPa. Significance The PICN material showed mechanical properties between porcelains and resin-based composites, reflecting its microstructural components. PMID:24656471

  9. Self-Healing of Unentangled Polymer Networks with Reversible Bonds

    PubMed Central

    Stukalin, Evgeny B.; Cai, Li-Heng; Kumar, N. Arun; Leibler, Ludwik; Rubinstein, Michael

    2013-01-01

    Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of unentangled polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess non-equilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. PMID:24347684

  10. Integrated Chemical Systems: The Simultaneous Formation of Hybrid Nanocomposites of Iron Oxide and Organo Silsesquioxanes

    SciTech Connect

    Zhao, L; Clapsaddle, B; Jr., J S; Schaefer, D; Shea, K

    2004-10-15

    A sol-gel approach for the synthesis of hybrid nanocomposites of iron oxide and bridged polysilsesquioxanes has been established. The procedures allow for the simultaneous formation of iron oxide and polysilsesquioxane networks in monolithic xerogels and aerogels. These hybrid nanocomposites are synthesized from FeCl{sub 3} {center_dot} 6H{sub 2}O and functionalized silsesquioxane monomers in a one-pot reaction using epoxides as a gelation agent. The porosity and microstructure of the materials has been determined by nitrogen porosimetry, electron microscopy and ultra small angle X-ray scattering (USAXS). The hybrid nanocomposites exhibit a uniform dispersion of both components with no evidence for phase separation at length scales > 5 nm. At this limit of resolution it is not possible to distinguish between two independent interpenetrating networks integrated at molecular length scales or a random copolymer or mixtures of both.

  11. Droplet formation and growth inside a polymer network: A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Jung, Jiyun; Jang, Eunseon; Shoaib, Mahbubul Alam; Jo, Kyubong; Kim, Jun Soo

    2016-04-01

    We present a molecular dynamics simulation study that focuses on the formation and growth of nanoscale droplets inside polymer networks. Droplet formation and growth are investigated by the liquid-vapor phase separation of a dilute Lennard-Jones (LJ) fluid inside regularly crosslinked, polymer networks with varying mesh sizes. In a polymer network with small mesh sizes, droplet formation can be suppressed, the extent of which is dependent on the attraction strength between the LJ particles. When droplets form in a polymer network with intermediate mesh sizes, subsequent growth is significantly slower when compared with that in bulk without a polymer network. Interestingly, droplet growth beyond the initial nucleation stage occurs by different mechanisms depending on the mesh size: droplets grow mainly by diffusion and coalescence inside polymer networks with large mesh sizes (as observed in bulk), whereas Ostwald ripening becomes a more dominant mechanism for droplet growth for small mesh sizes. The analysis of droplet trajectories clearly reveals the obstruction effect of the polymer network on the movement of growing droplets, which leads to Ostwald ripening of droplets. This study suggests how polymer networks can be used to control the growth of nanoscale droplets.

  12. Droplet formation and growth inside a polymer network: A molecular dynamics simulation study.

    PubMed

    Jung, Jiyun; Jang, Eunseon; Shoaib, Mahbubul Alam; Jo, Kyubong; Kim, Jun Soo

    2016-04-07

    We present a molecular dynamics simulation study that focuses on the formation and growth of nanoscale droplets inside polymer networks. Droplet formation and growth are investigated by the liquid-vapor phase separation of a dilute Lennard-Jones (LJ) fluid inside regularly crosslinked, polymer networks with varying mesh sizes. In a polymer network with small mesh sizes, droplet formation can be suppressed, the extent of which is dependent on the attraction strength between the LJ particles. When droplets form in a polymer network with intermediate mesh sizes, subsequent growth is significantly slower when compared with that in bulk without a polymer network. Interestingly, droplet growth beyond the initial nucleation stage occurs by different mechanisms depending on the mesh size: droplets grow mainly by diffusion and coalescence inside polymer networks with large mesh sizes (as observed in bulk), whereas Ostwald ripening becomes a more dominant mechanism for droplet growth for small mesh sizes. The analysis of droplet trajectories clearly reveals the obstruction effect of the polymer network on the movement of growing droplets, which leads to Ostwald ripening of droplets. This study suggests how polymer networks can be used to control the growth of nanoscale droplets.

  13. Copper-catalyzed azide alkyne cycloaddition polymer networks

    NASA Astrophysics Data System (ADS)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  14. Selective removal of heavy metal ions by disulfide linked polymer networks.

    PubMed

    Ko, Dongah; Lee, Joo Sung; Patel, Hasmukh A; Jakobsen, Mogens H; Hwang, Yuhoon; Yavuz, Cafer T; Hansen, Hans Chr Bruun; Andersen, Henrik R

    2017-03-06

    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions-copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

  15. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    DOE PAGES

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; ...

    2015-06-23

    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for furthermore » development of this new class of solid electrolytes.« less

  16. Simulation of Fracture Nucleation in Cross-Linked Polymer Networks

    NASA Astrophysics Data System (ADS)

    Moller, J. C.; Barr, S. A.; Schultz, E. J.; Breitzman, T. D.; Berry, R. J.

    2013-02-01

    A novel atomistic simulation method is developed whereby polymer systems can undergo strain-rate-controlled deformation while bond scission is enabled. The aim is to provide insight into the nanoscale origins of fracture. Various highly cross-linked epoxy systems including various resin chain lengths and levels of nonreactive dilution were examined. Consistent with the results of physical experiments, cured resin strength increased and ductility decreased with increasing cross-link density. An analysis of dihedral angle activity shows the locations in the molecular network that are most absorptive of mechanical energy. Bond scission occurred principally at cross-link sites as well as between phenyl rings in the bisphenol moiety. Scissions typically occurred well after yield and were accompanied by steady increases in void size and dihedral angle motion between bisphenol moieties and at cross-link sites. The methods developed here could be more broadly applied to explore and compare the atomistic nature of deformation for various polymers such that mechanical and fracture properties could be tuned in a rational way. This method and its results could become part of a solution system that spans multiple length and time scales and that could more completely represent such mechanical events as fracture.

  17. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    SciTech Connect

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.

    2015-06-23

    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for further development of this new class of solid electrolytes.

  18. Cascade synthesis of a gold nanoparticle-network polymer composite

    NASA Astrophysics Data System (ADS)

    Grubjesic, Simonida; Ringstrand, Bryan S.; Jungjohann, Katherine L.; Brombosz, Scott M.; Seifert, Sönke; Firestone, Millicent A.

    2016-01-01

    The multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate end-derivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4]-, formation of large aggregated Au NPs and oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multi-lamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Optical spectroscopy shows a notable red shift (Δλ ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.The multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical

  19. Modeling Methane Adsorption in Interpenetrating Porous Polymer Networks

    SciTech Connect

    Martin, RL; Shahrak, MN; Swisher, JA; Simon, CM; Sculley, JP; Zhou, HC; Smit, B; Haranczyk, M

    2013-10-03

    Porous polymer networks (PPNs) are a class of porous materials of particular interest in a variety of energy-related applications because of their stability, high surface areas, and gas uptake capacities. Computationally derived structures for five recently synthesized PPN frameworks, PPN-2, -3, -4, -5, and -6, were generated for various topologies, optimized using semiempirical electronic structure methods, and evaluated using classical grand canonical Monte Carlo simulations. We show that a key factor in modeling the methane uptake performance of these materials is whether, and how, these material frameworks interpenetrate and demonstrate a computational approach for predicting the presence, degree, and nature of interpenetration in PPNs that enables the reproduction of experimental adsorption data.

  20. Cascade synthesis of a gold nanoparticle–network polymer composite

    SciTech Connect

    Grubjesic, Simonida; Ringstrand, Bryan Scott; Jungjohann, Katherine L.; Brombosz, Scott M.; Seifert, Sönke; Firestone, Millicent Anne

    2015-11-02

    In this paper, the multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate endderivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4]-, formation of large aggregated Au NPs and oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multilamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Finally, optical spectroscopy shows a notable red shift (Δλ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.

  1. Cascade synthesis of a gold nanoparticle-network polymer composite

    SciTech Connect

    Grubjesic, Simonida; Ringstrand, Bryan Scott; Jungjohann, Katherine L.; Brombosz, Scott M.; Seifert, Sonke; Firestone, Millicent Anne

    2015-11-02

    In this paper, the multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate endderivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4]-, formation of large aggregated Au NPs and oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multilamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Finally, optical spectroscopy shows a notable red shift (Δλ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.

  2. Fast Switching of Vertical Alignment Liquid Crystal Cells with Liquid Crystalline Polymer Networks

    NASA Astrophysics Data System (ADS)

    Baek, Jong-In; Kim, Ki-Han; Kim, Jae Chang; Yoon, Tae-Hoon; Woo, Hwa Sung; Shin, Sung Tae; Souk, Jun Hyung

    2009-05-01

    This paper reports on the electro-optic characteristics of vertical alignment (VA) liquid crystal (LC) cells with liquid crystalline polymer networks. Optical bouncing, that occurs during the turn-on of VA cells, can be eliminated by introducing in-cell polymer networks. Furthermore, the turn-off also becomes much faster because of the anchoring effect caused by the anisotropy in the molecular shape of the liquid crystalline polymers. These response times have been found to vary for different LC/prepolymer mixtures. When the concentration of the liquid crystalline prepolymer in the initial LC/prepolymer mixture was 3, 5, or 10 wt %, the response times were measured to be 34, 56, and 87% faster than those of a VA cell with pure LC. These switching behaviors of VA cells with liquid crystalline polymer networks are demonstrated and compared with those using pure LC and with polymer networks made of isotropic prepolymers.

  3. Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions

    PubMed Central

    Benmouna, Farida; Zemmour, Samira; Benmouna, Mustapha

    2016-01-01

    ABSTRACT Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices. PMID:27134310

  4. Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions.

    PubMed

    Benmouna, Farida; Zemmour, Samira; Benmouna, Mustapha

    2016-03-03

    Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices.

  5. Recycling of textile dye using double network polymer from sodium alginate and superabsorbent polymer.

    PubMed

    Dhanapal, V; Subramanian, K

    2014-08-08

    Double network polymers (DNP) of different compositions were photosynthesized using sodium alginate (NaAlg) and superabsorbent polymer (SAP). They were characterized by FT-IR, thermal stability (TG), morphology by scanning electron microscopy (SEM), and its mechanical properties were also evaluated for their dye adsorption-desorption characteristics via adsorption isotherms at different temperature and pH values. The spectrophotometric determination of adsorbed dye indicated that the maximum dye uptake in column mode was 439 mg/g. The nearly identical visible absorption spectra of the fabrics dyed with virgin and recovered dyes indicated that the recovered dye retained its structural stability during column recovery and the dyed fabrics possess good color fastness properties. Dye adsorption kinetic and de-sorption mechanism were found to be pseudo-first-order and non-Fickian, respectively. The adsorption showed best fit for Langmuir adsorption isotherm. The changes in the thermodynamic parameters namely Gibbs free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) for the dye-adsorbent systems inferred that the adsorption process was spontaneous and exothermic.

  6. Surface modification of polyhedral oligomeric silsesquioxane block copolymer films by 157 nm laser light

    NASA Astrophysics Data System (ADS)

    Sarantopoulou, Evangelia; Kollia, Zoe; Cefalas, Alkiviadis Constantinos; Siokou, Ageliki Elina; Argitis, Panagiotis; Bellas, Vassilios; Kobe, Spomenka

    2009-06-01

    Thin films of ethyl polyhedral oligomeric silsesquioxane (ethyl-POSS) containing polymers at different compositions were chemically modified using laser irradiation at 157 nm. The irradiation caused photodissociation of C-O and C-H bonds followed by the formation of new chemical bonds. The content of Si-O and C-O bonds increased, as did the surface hardness. Vacuum ultraviolet (VUV) absorption, mass spectrometry, x-ray photoelectron spectroscopy, and atomic force microscopy imaging and indentation were used to evaluate the effects of the 157 nm irradiation. The chemical modification was restricted to a thin surface layer. The layer depth was determined by the penetration depth of the 157 nm VUV photons inside the thin copolymer layer. With prolonged VUV irradiation, the absorbance of the polymers increased, eventually becoming saturated. The chemical changes were accompanied by surface hardening, as evidenced by the increase in the Young's modulus from 4 to 24 GPa due to glassification of the irradiated parts. The chemically modified layer acts as a shield against photodissociation and degradation of the deeper portion of the POSS polymer by VUV radiation. Applications include the protection of solar cells on low orbit satellites from solar VUV photons.

  7. Surfactant self-assembly in oppositely charged polymer networks. Theory.

    PubMed

    Hansson, Per

    2009-10-01

    The interaction of ionic surfactants with polyion networks of opposite charge in an aqueous environment is analyzed theoretically by applying a recent theory of surfactant ion-polyion complex salts (J. Colloid. Int. Sci. 2009, 332, 183). The theory takes into account attractive and repulsive polyion-mediated interactions between the micelles, the deformation of the polymer network, the mixing of micelles, polyion chains, and simple ions with water, and the hydrophobic free energy at the micelle surface. The theory is used to calculate binding isotherms, swelling isotherms, surfactant aggregation numbers, compositions of complexes,and phase structure under various conditions. Factors controlling the gel volume transition and conditions for core/shell phase coexistence are investigated in detail, as well as the influence of salt. In particular, the interplay between electrostatic and elastic interactions is highlighted. Results from theory are compared with experimental data reported in the literature. The agreement is found to be semiquantitative or qualitative. The theory explains both the discrete volume transition observed in systems where the surfactant is in excess over the polyion and the core/shell phase coexistence in systems where the polyion is in excess.

  8. Fluorinated Polyhedral Oligomeric Silsesquioxanes (FluoroPOSS)

    DTIC Science & Technology

    2004-04-01

    Fluorodecyl(8T8), Contact Angle of Water on Fluorodecyl POSS Surface, Contact Angle of Mercury on Fluorodecyl POSS Surface, AFM Image of Spin-Cast...Fluorodecyl(8T8) Surface, Surface Energy of Fluorosiloxanes, Contact Angle and Chain Length, POSS Polymer Incorporation, Importance of R groups: Affect...compatibility with polymer matrix, PVDF/Fluoroocytl(8T8) POSS,PVDF/Fluoroocytl(nTn) POSS, Fluorinated Ethylene/Propylene, Poly(chlorotrifluoroethylene), Amorphous FEP, Water Contact Angle .

  9. Fluorinated and Thermo-Cross-Linked Polyhedral Oligomeric Silsesquioxanes: New Organic-Inorganic Hybrid Materials for High-Performance Dielectric Application.

    PubMed

    Wang, Jiajia; Sun, Jing; Zhou, Junfeng; Jin, Kaikai; Fang, Qiang

    2017-04-12

    A fluorinated and thermo-cross-linked polyhedral oligomeric silsesquioxane (POSS) has been successfully synthesized by thermal polymerization of a fluorinated POSS monomer having an inorganic silsesquioxane core and organic side chains bearing thermo-cross-linkable trifluorovinyl ether groups. This new inorganic-organic hybrid polymer shows high thermostability with a 5 wt % loss temperature of 436 °C, as well as good transparency (a sheet with an average thickness of 1.5 mm shows high transmittance of 92% varying from 400 to 1100 nm). Moreover, the polymer exhibits both low dielectric constant (<2.56) and low dissipation factor (<3.1 × 10(-3)) in a wide range of frequencies from 40 Hz to 30 MHz even at a high frequency of 5 GHz. The polymer also shows low water uptake (<0.04%) and low Dk (near 2.63) after immersing it in water at room temperature for 3 days. These data imply that this polymer is very suitable to be utilized as a high-performance dielectric material for fabrication of high-frequency printed circuit boards or encapsulation resins for integrated circuit dies in the microelectronic industry. Furthermore, this work also provides a route for the preparation of fluorinated POSS-based polymers.

  10. Polymer network/carbon layer on monolith support and monolith catalytic reactor

    DOEpatents

    Nordquist, Andrew Francis; Wilhelm, Frederick Carl; Waller, Francis Joseph; Machado, Reinaldo Mario

    2003-08-26

    The present invention relates to an improved monolith catalytic reactor and a monolith support. The improvement in the support resides in a polymer network/carbon coating applied to the surface of a porous substrate and a catalytic metal, preferably a transition metal catalyst applied to the surface of the polymer network/carbon coating. The monolith support has from 100 to 800 cells per square inch and a polymer network/carbon coating with surface area of from 0.1 to 15 m.sup.2 /gram as measured by adsorption of N.sub.2 or Kr using the BET method.

  11. Study of different routes to develop asymmetric double decker silsesquioxane (DDSQ)

    NASA Astrophysics Data System (ADS)

    Attanayake, Gayanthi Kumari

    Silsesquioxane cages can be considered as well-defined nanosized molecules (1-3 nm) and have attracted widening interests due to their possible use as components of resourceful inorganic/organic hybrid materials, as well as their applications in optics, catalysis, polymers and electronics. Double-decker silsesquioxane (DDSQ) nanoparticles have attracted much attention recently due to the ease of which these particles can be incorporated into polymeric materials and their unique capability to reinforce polymers.These systems are of high interest to scientists, due to their unique chemical and physical properties (solubility, non-flammability, oxidation resistance, and very good dielectric properties). For example, the United States Air Force and NASA use DDSQ incorporated polymers as thermoset material and flame retardants. This thesis discussed mainly three projects. One project centered on the research to improve and optimize the synthetic routes for a large scale synthesis of DDSQ functionalized oligoimides. These procedures offer the opportunity to combine several synthetic steps into a single reaction vessel, thereby cutting processing time and costs. The second project discussed is on the synthesis of a novel (phenylethynyl)phenyl DDSQ oligomer that can be used for high temperature application. This oligomer was successfully synthesized through a one pot route with 70% yield by avoiding the tedious separation techniques, fractional distillations and Kugelroher distillation. This novel oligomer will be characterized using TGA (Thermal Gravimetric Analysis) and DSC (Differential Scanning Calorimetry) for future studies. Another novel synthetic approach towards the synthesis of (phenylethynyl)phenyl DDSQ oligomers is also discussed. This new approach was based on Pd-catalyzed silylation of aryl halides. Even though Pd-catalyzed silylation of aryl halides was successful for the T7(iBu) cage, this chemistry was not applicable for DDSQ-H cage. The main project was

  12. Predictive Methods for Dense Polymer Networks: Combating Bias with Bio-Based Structures

    DTIC Science & Technology

    2016-03-16

    Briefing Charts 3. DATES COVERED (From - To) 24 February 2016 – 18 March 2016 4. TITLE AND SUBTITLE Predictive methods for dense polymer networks...PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NO. Air Force Research Laboratory (AFMC) AFRL/RQRP 10 E. Saturn...unlimited. PA Clearance 16152 Integrity  Service  Excellence Predictive methods for dense polymer networks: Combating bias with bio-based

  13. Pattern Formations in Polymer-Molecular Motor Networks

    NASA Astrophysics Data System (ADS)

    Smith, David; Humphrey, David; Duggan, Cynthia; Käs, Josef

    2001-03-01

    In previous studies with the microtubule-kinesin system, organized patterns such as asters and rotating vortices have been seen (Nedelec et al, Nature 1997), which were of a dynamic nature and dependent on active motors. A similar system was constructed using actin and myosin, which displays similar patterns, however, with drastically different dynamics. These patterns arise independent of the initial amount of immediate use energy (in the form of ATP), assembling only upon the near exhaustion of available ATP. Further studies have clearly shown that in fact these patterns are not dependent upon the motor activity of the myosin but its propensity to serve as a cross-linking element in an actin network, with the motor activity serving to prevent the arising of order in the system. We believe the dynamic differences inherent between the two polymer-motor systems studied lies primarily in the structural nature of the motor complexes, with the kinesin complex ordering the system by pushing multiple filaments in a parallel direction, and the myosin complexes disordering the system by pushing filaments in an antiparallel manner.

  14. Cytotoxicity and genotoxicity of superporous hydrogel containing interpenetrating polymer networks.

    PubMed

    Yin, Lichen; Zhao, Xin; Cui, Liming; Ding, Jieying; He, Miao; Tang, Cui; Yin, Chunhua

    2009-06-01

    The superporous hydrogel containing poly(acrylic acid-co-acrylamide)/O-carboxymethyl chitosan (O-CMC) interpenetrating polymer networks (SPH-IPN) that had been developed as an oral delivery vehicle for protein drugs was subject to cytotoxicity and genotoxicity testing, thus evaluating its biological safety in use. In a battery of cytotoxicity assays on RBL-2H3 and Caco-2 cells, the SPH-IPN caused minimal damage towards cell viability, lysosomal activity, and metabolic activity following both direct and indirect treatment. The SPH-IPN did not induce cell apoptosis or DNA breakage in the above cell lines; it did not increase micronucleus (MN) incidence in mouse bone marrow, either. Therefore, the SPH-IPN was preliminarily considered to be biocompatible and might be a safe carrier for protein drugs. In addition, using the HPLC method, residual acrylic acid, acrylamide, and glutaraldehyde in the SPH-IPN were quantified to be 1.4, 2.0, and below 0.2 ppm, respectively. Lack of these low molecular monomers and crosslinker that were mainly responsible for the toxicity provided evidence for the good biocompatibility of the SPH-IPN.

  15. Morphology effect on the light scattering and dynamic response of polymer network liquid crystal phase modulator.

    PubMed

    Xiangjie, Zhao; Cangli, Liu; Jiazhu, Duan; Jiancheng, Zeng; Dayong, Zhang; Yongquan, Luo

    2014-06-16

    Polymer network liquid crystal (PNLC) was one of the most potential liquid crystal for submillisecond response phase modulation, which was possible to be applied in submillisecond response phase only spatial light modulator. But until now the light scattering when liquid crystal director was reoriented by external electric field limited its phase modulation application. Dynamic response of phase change when high voltage was applied was also not elucidated. The mechanism that determines the light scattering was studied by analyzing the polymer network morphology by SEM method. Samples were prepared by varying the polymerization temperature, UV curing intensity and polymerization time. The morphology effect on the dynamic response of phase change was studied, in which high voltage was usually applied and electro-striction effect was often induced. The experimental results indicate that the polymer network morphology was mainly characterized by cross linked single fibrils, cross linked fibril bundles or even both. Although the formation of fibril bundle usually induced large light scattering, such a polymer network could endure higher voltage. In contrast, although the formation of cross linked single fibrils induced small light scattering, such a polymer network cannot endure higher voltage. There is a tradeoff between the light scattering and high voltage endurance. The electro-optical properties such as threshold voltage and response time were taken to verify our conclusion. For future application, the monomer molecular structure, the liquid crystal solvent and the polymerization conditions should be optimized to generate optimal polymer network morphology.

  16. Probing Rubber Cross-Linking Generation of Industrial Polymer Networks at Nanometer Scale.

    PubMed

    Gabrielle, Brice; Gomez, Emmanuel; Korb, Jean-Pierre

    2016-06-23

    We present improved analyses of rheometric torque measurements as well as (1)H double-quantum (DQ) nuclear magnetic resonance (NMR) buildup data on polymer networks of industrial compounds. This latter DQ NMR analysis allows finding the distribution of an orientation order parameter (Dres) resulting from the noncomplete averaging of proton dipole-dipole couplings within the cross-linked polymer chains. We investigate the influence of the formulation (filler and vulcanization systems) as well as the process (curing temperature) ending to the final polymer network. We show that DQ NMR follows the generation of the polymer network during the vulcanization process from a heterogeneous network to a very homogeneous one. The time variations of microscopic Dres and macroscopic rheometric torques present power-law behaviors above a threshold time scale with characteristic exponents of the percolation theory. We observe also a very good linear correlation between the kinetics of Dres and rheometric data routinely performed in industry. All these observations confirm the description of the polymer network generation as a critical phenomenon. On the basis of all these results, we believe that DQ NMR could become a valuable tool for investigating in situ the cross-linking of industrial polymer networks at the nanometer scale.

  17. Cardiovascular application of polyhedral oligomeric silsesquioxane nanomaterials: a glimpse into prospective horizons

    PubMed Central

    Ghanbari, Hossein; de Mel, Achala; Seifalian, Alexander M

    2011-01-01

    Revolutionary advances in nanotechnology propose novel materials with superior properties for biomedical application. One of the most promising nanomaterials for biomedical application is polyhedral oligomeric silsesquioxane (POSS), an amazing nanocage consisting of an inner inorganic framework of silicon and oxygen atoms and an outer shell of organic groups. The unique properties of this nanoparticle has led to the development of a wide range of nanostructured copolymers with significantly enhanced properties including improved mechanical, chemical, and physical characteristics. Since POSS nanomaterials are highly biocompatible, biomedical application of POSS nanostructures has been intensely explored. One of the most promising areas of application of POSS nanomaterials is the development of cardiovascular implants. The incorporation of POSS into biocompatible polymers has resulted in advanced nanocomposite materials with improved hemocompatibility, antithrombogenicity, enhanced mechanical and surface properties, calcification resistance, and reduced inflammatory response, which make these materials the material of choice for cardiovascular implants. These highly versatile POSS derivatives have opened new horizons to the field of cardiovascular implant. Currently, application of POSS containing polymers in the development of new generation cardiovascular implants including heart valve prostheses, bypass grafts, and coronary stents is under intensive investigation, with encouraging outcomes. PMID:21589645

  18. Biodegradability of regenerated cellulose films coated with polyurethane/natural polymers interpenetrating polymer networks

    SciTech Connect

    Zhang, L.; Zhou, J.; Huang, J.; Gong, P. Zhou, Q.; Zheng, L.; Du, Y.

    1999-11-01

    Interpenetrating polymer network (IPN) coatings synthesized from castor-oil-based polyurethane (PU) with chitosan, nitrocellulose, or elaeostearin were coated on regenerated cellulose (RC) film for curing at 80--100 C for 2--5 min, providing biodegradable, water-resistant cellulose films coded, respectively, as RCCH, RCNC, and RCEs. The coated films were buried in natural soil for decaying and inoculated with a spore suspension of fungi on the agar medium, respectively, to test biodegradability. The viscosity-average molecular weight, M{sub {eta}}, and the weight of the degraded films decreased sharply with the progress of degradation. The degradation half-lifes, t{sub 1/2}, of the films in soil at 30 C were found to be 19 days for RC, 25 days for RCNC, 32 days for RCCH, and 45 days for the RCEs films. Scanning electron microscopy (SEM) showed that the extent of decay followed in the order RC {gt} RCNC {gt} RCCH {gt} RCEs. SEM, infrared (IR), high-performance liquid chromatography (HPLC), and CO{sub 2} evolution results indicated that the microorganisms directly attacked the water-resistant coating layer and then penetrated into the cellulose to speedily metabolize, while accompanying with producing CO{sub 2}, H{sub 2}O, glucose cleaved from cellulose, and small molecules decomposed from the coatings.

  19. Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS)

    DTIC Science & Technology

    2010-02-01

    as their polymer composites, will be discussed. 1. INTRODUCTION Fluorinated compounds are a logical choice for hydrophobic applications due to...grabbing software coupled to a CCD camera operating at the optimized zoom and contrast. The contact angles were determined via the software suite...A. Gakh, A. A. Tuinman, J. L. Adcock, R. A. Sachleben, R. N. Compton , Am. Chem. Soc. J., 116, 819 (1994). 2. P. J. Fagan, P. J. Krusic, C. N. McEwen

  20. Hybrid polymer networks as ultra low `k` dielectric layers

    DOEpatents

    Lewicki, James; Worsley, Marcus A.

    2016-02-16

    According to one embodiment, a polymeric material includes at least one polydimethylsiloxane (PDMS) polymer, and at least one polyhedral oligomericsilsequioxane (POSS) molecule. According to another embodiment, a method includes providing at least one polydimethylsiloxane (PDMS) polymer, providing at least one polyhedral oligomericsilsequioxane (POSS) molecule, and coupling the at least one PDSM polymer to the at least one POSS molecule to form a hybrid polymeric material.

  1. Dynamic Covalent Polymer Networks: from Old Chemistry to Modern Day Innovations.

    PubMed

    Zou, Weike; Dong, Jiante; Luo, Yingwu; Zhao, Qian; Xie, Tao

    2017-04-01

    Dynamic covalent polymer networks have long been recognized. With the initial focus on the unintended impact of dynamic covalent linkages on the viscoelasticity of commercial rubbers, efforts in modern times have transitioned into designing dynamic covalent polymer networks with unique adaptive properties. Whereas self-healing and thermoset reprocessing have been the primary motivations for studying dynamic covalent polymer networks, the recent discovery of the vitrimeric rheological behavior and solid-state plasticity for this type of material have opened up new opportunities in material innovations. This, coupled with the revelation of the dynamic characteristics of commercially relevant polymer building blocks such as esters and urethanes, suggests a promising future for this class of materials.

  2. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    DOE PAGES

    Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; ...

    2015-04-24

    In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks).more » The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.« less

  3. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    SciTech Connect

    Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; Henderson, Ian M.; Bouxsein, Nathan F.

    2015-04-24

    In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.

  4. Morphological control of inter-penetrating polymer networks

    NASA Technical Reports Server (NTRS)

    Hansen, Marion

    1989-01-01

    Synthetic organic polymer chemistry has been successful in producing composition of matter with thermal oxidation stability and progressively higher glass transition temperatures. In part, this was done by increasing the steric-hindrance of moieties in the chain of a macromolecule. The resulting polymers are usually quite insoluble and produce molten polymers of very high viscosities. These types of polymers are not easily processed into graphite fiber prepregs by melt or solution impregnation methods. Hence, a technological need exists to produce new knowledge of how to produce polymer-fiber composites from this class of polymers. The concept of freeze drying amic-acid prepolymers with reactive thermoplastic was proposed as a research topic for the ASEE/NASA Summer Faculty Program of 1989 as a means of producing polymer-fiber composites. This process scheme has the thermodynamic attribute that the magnitude of phase separation due to differences in solubility of two organic constituents in solution will be greatly reduced by removing a solvent not by evaporation but by sublimation. Progress to date on evaluating this polymer processing concept is briefly outlined.

  5. Dynamics of comb-of-comb-network polymers in random layered flows.

    PubMed

    Katyal, Divya; Kant, Rama

    2016-12-01

    We analyze the dynamics of comb-of-comb-network polymers in the presence of external random flows. The dynamics of such structures is evaluated through relevant physical quantities, viz., average square displacement (ASD) and the velocity autocorrelation function (VACF). We focus on comparing the dynamics of the comb-of-comb network with the linear polymer. The present work displays an anomalous diffusive behavior of this flexible network in the random layered flows. The effect of the polymer topology on the dynamics is analyzed by varying the number of generations and branch lengths in these networks. In addition, we investigate the influence of external flow on the dynamics by varying flow parameters, like the flow exponent α and flow strength W_{α}. Our analysis highlights two anomalous power-law regimes, viz., subdiffusive (intermediate-time polymer stretching and flow-induced diffusion) and superdiffusive (long-time flow-induced diffusion). The anomalous long-time dynamics is governed by the temporal exponent ν of ASD, viz., ν=2-α/2. Compared to a linear polymer, the comb-of-comb network shows a shorter crossover time (from the subdiffusive to superdiffusive regime) but a reduced magnitude of ASD. Our theory displays an anomalous VACF in the random layered flows that scales as t^{-α/2}. We show that the network with greater total mass moves faster.

  6. Dynamics of comb-of-comb-network polymers in random layered flows

    NASA Astrophysics Data System (ADS)

    Katyal, Divya; Kant, Rama

    2016-12-01

    We analyze the dynamics of comb-of-comb-network polymers in the presence of external random flows. The dynamics of such structures is evaluated through relevant physical quantities, viz., average square displacement (ASD) and the velocity autocorrelation function (VACF). We focus on comparing the dynamics of the comb-of-comb network with the linear polymer. The present work displays an anomalous diffusive behavior of this flexible network in the random layered flows. The effect of the polymer topology on the dynamics is analyzed by varying the number of generations and branch lengths in these networks. In addition, we investigate the influence of external flow on the dynamics by varying flow parameters, like the flow exponent α and flow strength Wα. Our analysis highlights two anomalous power-law regimes, viz., subdiffusive (intermediate-time polymer stretching and flow-induced diffusion) and superdiffusive (long-time flow-induced diffusion). The anomalous long-time dynamics is governed by the temporal exponent ν of ASD, viz., ν =2 -α /2 . Compared to a linear polymer, the comb-of-comb network shows a shorter crossover time (from the subdiffusive to superdiffusive regime) but a reduced magnitude of ASD. Our theory displays an anomalous VACF in the random layered flows that scales as t-α /2. We show that the network with greater total mass moves faster.

  7. Novel silsesquioxane mixture-modified high elongation polyurethane with reduced platelet adhesion

    NASA Astrophysics Data System (ADS)

    Tao, William; Zhou, Hongyang; Zhang, Yan; Li, Gang

    2008-02-01

    We have successfully synthesized a kind of novel silsesquioxane mixture that can be used to modify the surface of biomaterial polyurethane (PU) for the purpose of making silsesquioxane/PU as low-price and high-quality biomaterial. HPLC, FTIR and 29Si NMR are used to characterize as-synthesized silsesquioxane mixture. XPS figure and SEM images show the silsesquioxane particles really self-assemble on the PU surface. Contact angle measurements verify that there is a large hysteresis loop, which relates to low- and high-surface free energy component on the surface. Platelet adsorption at 90 min of PU/silsesquioxane mixture is lower than that of poly(tetrafluoroethylene) (PTFE) and PU (two-way ANOVA, p < 0.05). Furthermore, SEM images show "island" morphologic pattern with Cooper grades I platelet adsorption morphology on the smooth PU/silsesquioxane surface, and mechanic test shows that the samples with silsesquioxane mixture can increase mechanic property of PU. On the basis of these results, we conclude that this kind of nanocomposite has promise for application in biomaterials.

  8. Classical Challenges in the Physical Chemistry of Polymer Networks and the Design of New Materials.

    PubMed

    Wang, Rui; Sing, Michelle K; Avery, Reginald K; Souza, Bruno S; Kim, Minkyu; Olsen, Bradley D

    2016-12-20

    Polymer networks are widely used from commodity to biomedical materials. The space-spanning, net-like structure gives polymer networks their advantageous mechanical and dynamic properties, the most essential factor that governs their responses to external electrical, thermal, and chemical stimuli. Despite the ubiquity of applications and a century of active research on these materials, the way that chemistry and processing interact to yield the final structure and the material properties of polymer networks is not fully understood, which leads to a number of classical challenges in the physical chemistry of gels. Fundamentally, it is not yet possible to quantitatively predict the mechanical response of a polymer network based on its chemical design, limiting our ability to understand and characterize the nanostructure of gels and rationally design new materials. In this Account, we summarize our recent theoretical and experimental approaches to study the physical chemistry of polymer networks. First, our understanding of the impact of molecular defects on topology and elasticity of polymer networks is discussed. By systematically incorporating the effects of different orders of loop structure, we develop a kinetic graph theory and real elastic network theory that bridge the chemical design, the network topology, and the mechanical properties of the gel. These theories show good agreement with the recent experimental data without any fitting parameters. Next, associative polymer gel dynamics is discussed, focusing on our evolving understanding of the effect of transient bonds on the mechanical response. Using forced Rayleigh scattering (FRS), we are able to probe diffusivity across a wide range of length and time scales in gels. A superdiffusive region is observed in different associative network systems, which can be captured by a two-state kinetic model. Further, the effects of the architecture and chemistry of polymer chains on gel nanostructure are studied. By

  9. Syntheses of silsesquioxane (POSS)-based inorganic/organic hybrid and the application in reinforcement for an epoxy resin.

    PubMed

    Ni, Caihua; Ni, Guifeng; Zhang, Liping; Mi, Jiaquan; Yao, Bolong; Zhu, Changping

    2011-10-01

    A new inorganic/organic hybrid material containing silsesquioxane was prepared by the reaction of caged octa (aminopropyl silsesquioxane) (POSS-NH(2)) with n-butyl glycidyl ether (nBGE) and 1,4-butanediol diglycidyl ether (BDGE). The copolymers of POSS, nBGE, and BDGE could be obtained with varied feed ratio of POSS-NH(2), nBGE, and BDGE in the preparation. The hybrid material was added into an epoxy resin (E51) for enhancing the toughening and thermal properties of the epoxy resin. The results showed that the toughening and the thermal properties of the cured epoxy resin were greatly improved by the addition of the hybrid. The enhancement was ascribed to nano-scale effect of the POSS structure and the formation of anchor structure in the cured network. The investigation of kinetics for the curing process of the hybrid-modified epoxy resin revealed that two kinds of curing reactions occurred in different temperature ranges. They were attributed to the reactions between amino groups of the curing agent with epoxy groups of E51 and with residue epoxy groups in the hybrid. The reacting activation energies were calculated based on Kissinger's and Flynn-Wall-Ozawa's methods, respectively.

  10. Multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes nanocomposite preparation via cross-linking reaction in acidic media

    NASA Astrophysics Data System (ADS)

    Somasekharan, Lakshmipriya; Thomas, Sabu; Comoy, Corinne; Sivasankarapillai, Anilkumar; Kalarikkal, Nandakumar; Lamouroux, Emmanuel

    2016-11-01

    Multiwalled carbon nanotubes have unique properties allowing their use in a wide range of applications—from microelectronics to biomedical and polymer fields. Nevertheless, a crucial aspect for their use resides in the ease of handling them during the process. Here, we report a facile route to prepare multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes (MWCNT@POSS) nanocomposite. The method involves the formation of a covalent bond between carboxylated MWCNTs and OV-POSS using acid-catalyzed electrophilic addition reaction. The resulting nanocomposite have been characterized by Fourier transform infrared spectroscopy (FTIR), powder X-Ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results confirmed that the formation of MWCNT@POSS nanocomposite did not deteriorate MWCNT structure or morphology. Here, we used a 1:1 ratio of carboxylated MWCNTs and OV-POSS and the POSS content in the nanocomposite was 39.5 wt%.

  11. Relationship of Polymer Molecular Weight and Cure Temperature in Photopolymerization-Induced Phase Separation of Liquid Crystal and Polymer Fiber Networks

    NASA Astrophysics Data System (ADS)

    Murashige, Takeshi; Fujikake, Hideo; Ikehata, Seiichiro; Sato, Fumio

    2002-10-01

    We studied the dependence of polymer molecular weight on cure temperature in the photopolymerization-induced phase separation of liquid crystal and polymer fiber networks, using gel permeation chromatography. As the experimental result, it was found for the first time that the molecular weight of the polymer, which is segregated and aggregated in the solution of monomer and the liquid crystal, increases with decreasing the temperature. We considered that the spatial concentration of growing polymer density, which is induced by the phase separation with the temperature decrease, accelerates the chemical bonding of polymer molecules.

  12. Light-emitting conjugated polymers with microporous network architecture: interweaving scaffold promotes electronic conjugation, facilitates exciton migration, and improves luminescence.

    PubMed

    Xu, Yanhong; Chen, Long; Guo, Zhaoqi; Nagai, Atsushi; Jiang, Donglin

    2011-11-09

    Herein we report a strategy for the design of highly luminescent conjugated polymers by restricting rotation of the polymer building blocks through a microporous network architecture. We demonstrate this concept using tetraphenylethene (TPE) as a building block to construct a light-emitting conjugated microporous polymer. The interlocked network successfully restricted the rotation of the phenyl units, which are the major cause of fluorescence deactivation in TPE, thus providing intrinsic luminescence activity for the polymers. We show positive "CMP effects" that the network promotes π-conjugation, facilitates exciton migration, and improves luminescence activity. Although the monomer and linear polymer analogue in solvents are nonemissive, the network polymers are highly luminescent in various solvents and the solid state. Because emission losses due to rotation are ubiquitous among small chromophores, this strategy can be generalized for the de novo design of light-emitting materials by integrating the chromophores into an interlocked network architecture.

  13. Amphiphilic semi-interpenetrating polymer networks using pulverized rubber

    NASA Astrophysics Data System (ADS)

    Shahidi, Nima

    Scrap rubber materials provide a significant challenge to either reuse or safe disposal. Every year, millions of tires are discarded to landfills in the United States, consuming a staggering amount of land space, creating a high risk for large fires, breeding mosquitoes that spread diseases, and wasting the planet's natural resources. This situation cannot be sustained. The challenge of reusing scrap rubber materials is mainly due to the crosslinked structure of vulcanized rubber that prevent them from melting and further processing for reuse. The most feasible recycling approach is believed to be a process in which the vulcanized rubber is first pulverized into a fine powder and then incorporated into new products. The production of fine rubber particles is generally accomplished through the use of a cryogenic process that is costly. Therefore, development of a cost effective technology that utilizes a large quantity of the scrap rubber materials to produce high value added materials is an essential element in maintaining a sustainable solution to rubber recycling. In this research, a cost effective pulverization process, solid state shear extrusion (SSSE), was modified and used for continuous pulverization of the rubber into fine particles. In the modified SSSE process, pulverization takes place at high compressive shear forces and a controlled temperature. Furthermore, an innovative particle modification process was developed to enhance the chemical structure and surface properties of the rubber particles for manufacturing of high value added products. Modification of rubber particles was accomplished through the polymerization of a hydrophilic monomer mixture within the intermolecular structure of the hydrophobic rubber particles. The resulting composite particles are considered as amphiphilic particulate phase semi-interpenetrating polymer networks (PPSIPNs). The modified rubber particles are water dispersible and suitable for use in a variety of aqueous media

  14. Active fluidization of polymer networks through molecular motors.

    PubMed

    Humphrey, D; Duggan, C; Saha, D; Smith, D; Käs, J

    2002-03-28

    Entangled polymer solutions and melts exhibit elastic, solid-like resistance to quick deformations and a viscous, fluid-like response to slow deformations. This viscoelastic behaviour reflects the dynamics of individual polymer chains driven by brownian motion: since individual chains can only move in a snake-like fashion through the mesh of surrounding polymer molecules, their diffusive transport, described by reptation, is so slow that the relaxation of suddenly imposed stress is delayed. Entangled polymer solutions and melts therefore elastically resist deforming motions that occur faster than the stress relaxation time. Here we show that the protein myosin II permits active control over the viscoelastic behaviour of actin filament solutions. We find that when each actin filament in a polymerized actin solution interacts with at least one myosin minifilament, the stress relaxation time of the polymer solution is significantly shortened. We attribute this effect to myosin's action as a 'molecular motor', which allows it to interact with randomly oriented actin filaments and push them through the solution, thus enhancing longitudinal filament motion. By superseding reptation with sliding motion, the molecular motors thus overcome a fundamental principle of complex fluids: that only depolymerization makes an entangled, isotropic polymer solution fluid for quick deformations.

  15. Ferroelectric polymer networks with high energy density and improved discharged efficiency for dielectric energy storage.

    PubMed

    Khanchaitit, Paisan; Han, Kuo; Gadinski, Matthew R; Li, Qi; Wang, Qing

    2013-01-01

    Ferroelectric polymers are being actively explored as dielectric materials for electrical energy storage applications. However, their high dielectric constants and outstanding energy densities are accompanied by large dielectric loss due to ferroelectric hysteresis and electrical conduction, resulting in poor charge-discharge efficiencies under high electric fields. To address this long-standing problem, here we report the ferroelectric polymer networks exhibiting significantly reduced dielectric loss, superior polarization and greatly improved breakdown strength and reliability, while maintaining their fast discharge capability at a rate of microseconds. These concurrent improvements lead to unprecedented charge-discharge efficiencies and large values of the discharged energy density and also enable the operation of the ferroelectric polymers at elevated temperatures, which clearly outperforms the melt-extruded ferroelectric polymer films that represents the state of the art in dielectric polymers. The simplicity and scalability of the described method further suggest their potential for high energy density capacitors.

  16. Network of nano-droplets by a tri-block polymer

    NASA Astrophysics Data System (ADS)

    Sharifi, Soheil; Doodman, Esmaeil

    2014-11-01

    Mixtures of oil in water nano-droplets with two molecular weights of a tri-block polymer was studied by quasi elastic light scattering and small angle X-ray scattering. The results showed that the size and interaction of droplets didn't change with increase of the tri-block polymer length but the order parameters increased. The increase of length of the tri-block biopolymer changed the dynamics of the droplets. A network formation is resulted with increase of the amount of tri-block polymer in the microemulsions.

  17. Relaxation dynamics of small-world degree-distributed treelike polymer networks

    NASA Astrophysics Data System (ADS)

    Galiceanu, Mircea; Oliveira, Edieliton S.; Dolgushev, Maxim

    2016-11-01

    Hyperbranched polymers are typically treelike macromolecules with a very disordered structure. Here we construct hyperbranched polymers based on the degree distribution of the small-world networks. This algorithm allows us to study a transition from monodisperse linear chains to structurally-disordered dendritic polymers by varying the parameter p (0 ≤ p ≤ 1), which measures the randomness and the degree of branching of the network. Employing the framework of generalized Gaussian structures, we determine for the obtained structures the relaxation spectra, which are exemplified on the mechanical relaxation moduli (storage and loss moduli). We monitor these physical quantities for networks of different sizes and for various values of the parameter p. In the intermediate frequency domain, we encounter macroscopically distinguishable behaviours.

  18. Electroclinic effect in a chiral smectic-A liquid crystal stabilized by an anisotropic polymer network.

    PubMed

    Petit, Mohamed; Daoudi, Abdelylah; Ismaili, Mimoun; Buisine, Jean Marc

    2006-12-01

    We have studied the effect of an anisotropic polymer network on the coupling of molecular tilt to applied electric field in the chiral S{A} phase. The polymer network is formed from a photoreactive achiral monomer in a thin planar S{C}{*} cell. Experimental data, obtained from electro-optical measurements near to the S{A}-S{c}{*} transition temperature, T{c} , of the induced molecular tilt, switching time, as well as induced polarization as a function of temperature and electric field strength are presented. The results clearly show that, close to T{c} , the electroclinic effect is largely controlled by the polymer network. The experimental results are discussed in the framework of a simple phenomenological model, extended from the Landau model, which includes the bulk free energy arising from the anisotropic interaction between the polymer network and the liquid crystal director, and the elastic free energy resulting from the anchoring (supposed rigid) of the liquid crystal molecules at the polymer boundaries.

  19. pH-controlled nanoaggregation in amphiphilic polymer co-networks.

    PubMed

    Longo, Gabriel S; Olvera de la Cruz, Monica; Szleifer, Igal

    2013-03-26

    Domain formation and control in pH-responsive amphiphilic polymer co-networks are studied theoretically. Two different molecular architectures of the polymer network are considered, depending on whether the pH-sensitive motif is borne by the hydrophobic or the hydrophilic monomer. When the hydrophobic polymer contains acidic groups, such chains form nanometric aggregates at acidic conditions, but they are found in a swollen state at alkaline pH. At intermediate pH, the nanoaggregation behavior of the hydrophobic polymer depends critically on the environment salt concentration. Moreover, our results indicate the presence of microphase separation into domains of swollen and aggregated hydrophobic chains. If the hydrophilic polymer is the ionizable component of the network, the nanoaggregation of hydrophobic monomers is weakly dependent on the pH and salt concentration, and except at very low volume fraction, the aggregate is the most probable conformation of the network in the entire range of pH and salt concentration studied. The two different hydrogels display quantitatively similar swelling transition and apparent pKa, but at the nanoscale, their behavior is qualitatively different. The spatial distribution of electric charge on the network as well as the local density of the different chemical species within the hydrogel can be controlled, as a function of pH and salt concentration, by the molecular architecture of the polymer network. These findings have relevance for applications in biomaterials and nanotechnology, in particular, in the design of oral delivery devices for the administration of hydrophobic drugs.

  20. Investigation of the rheology and transport of polymers in porous media using network models

    SciTech Connect

    Sorbie, K.S.; Clifford, P.J.

    1988-05-01

    Polymers have been used in improved oil recovery operations as mobility control agents in surfactant and polymer flooding and in gel treatments. In order to predict the outcome of such processes, it is necessary to have a good understanding of the rheology and transport of polymer solutions in porous media. The rheological behavior refers essentially to the pressure drop/flow rate relationship observed for the polymer solution in the porous medium. It is relatively straightforward to measure rheological properties of bulk polymer solutions such as the viscosity/shear rate behavior or, for elastic fluids, the normal stress differences. However, the pressure drop/flow rate behavior of the polymers in flow through porous media may be either qualitatively quite similar or very different from bulk flow behavior as measured, for example, in a capillary viscometer. In both the rheology and dispersion behavior of polymers in porous media, they see that the phenomenon being observed macroscopically is a result of the interaction between a fluid or molecular property and the stochastic nature of the porous medium at the microscopic level. If one views the porous medium as a network of joined capillaries, then the rheological behavior in each capillary will be quite well defined, e.g. through a single constitutive relationship. In the investigation of hydrodynamic dispersion of polymer and tracer in porous media, the role of the stochastic nature of the medium is clearly evident.

  1. Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

    PubMed Central

    Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto

    2017-01-01

    In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels. PMID:28100492

  2. Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

    NASA Astrophysics Data System (ADS)

    Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto; Barker, Thomas H.

    2017-01-01

    In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels.

  3. Layered hybrid perovskites with micropores created by alkylammonium functional silsesquioxane interlayers.

    PubMed

    Kataoka, Sho; Banerjee, Subhabrata; Kawai, Akiko; Kamimura, Yoshihiro; Choi, Jun-Chul; Kodaira, Tetsuya; Sato, Kazuhiko; Endo, Akira

    2015-04-01

    Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

  4. Laplacian spectra of recursive treelike small-world polymer networks: Analytical solutions and applications

    NASA Astrophysics Data System (ADS)

    Liu, Hongxiao; Zhang, Zhongzhi

    2013-03-01

    A central issue in the study of polymer physics is to understand the relation between the geometrical properties of macromolecules and various dynamics, most of which are encoded in the Laplacian spectra of a related graph describing the macrostructural structure. In this paper, we introduce a family of treelike polymer networks with a parameter, which has the same size as the Vicsek fractals modeling regular hyperbranched polymers. We study some relevant properties of the networks and show that they have an exponentially decaying degree distribution and exhibit the small-world behavior. We then study the Laplacian eigenvalues and their corresponding eigenvectors of the networks under consideration, with both quantities being determined through the recursive relations deduced from the network structure. Using the obtained recursive relations we can find all the eigenvalues and eigenvectors for the networks with any size. Finally, as some applications, we use the eigenvalues to study analytically or semi-analytically three dynamical processes occurring in the networks, including random walks, relaxation dynamics in the framework of generalized Gaussian structure, as well as the fluorescence depolarization under quasiresonant energy transfer. Moreover, we compare the results with those corresponding to Vicsek fractals, and show that the dynamics differ greatly for the two network families, which thus enables us to distinguish between them.

  5. Tuning mechanical properties of polymer-grafted nanoparticle networks by using biomimetic catch bonds

    NASA Astrophysics Data System (ADS)

    Mbanga, Badel L.; Iyer, Balaji V. S.; Yashin, Victor V.; Balazs, Anna C.

    Cross-linked networks of polymer-grafted nanoparticles (PGNs) constitute a class of composites with tunable mechanical properties that exhibit a self-healing behavior. A PGN network consists of nanoparticles that are decorated with end-grafted polymer chains. Reactive groups on the free ends of these grafted chains can form bonds with the chain ends on the nearby particles. We study these materials using a 3D computational model that encompasses the particle-particle interactions, the kinetics of bond formation and rupture, and the external forces applied to the network. In our model, a fraction of cross-links is formed through biomimetic ``catch'' bonds. In contrast to conventional ``slip'' bonds, catch bonds can effectively become stronger under a deformation. We show that by varying the fraction of these catch bonds in the network, the toughness, ductility, and tensile strength of the material could be tuned to desired levels.

  6. Modeling of polymer networks for application to solid propellant formulating

    NASA Technical Reports Server (NTRS)

    Marsh, H. E.

    1979-01-01

    Methods for predicting the network structural characteristics formed by the curing of pourable elastomers were presented; as well as the logic which was applied in the development of mathematical models. A universal approach for modeling was developed and verified by comparison with other methods in application to a complex system. Several applications of network models to practical problems are described.

  7. Polyhedral oligomeric silsesquioxanes as modifiers of polyoxymethylene structure

    NASA Astrophysics Data System (ADS)

    Czarnecka-Komorowska, Dorota; Sterzynski, Tomasz; Dutkiewicz, Michal

    2015-12-01

    In this paper the influence of silsesquioxanes (POSS) on crystallization behaviour of polyoxymethylene (POM) during non-isothermal crystallization was investigated by polarized light microscope (PLM) and differential scanning calorimetry (DSC). The study concerns polyoxymethylene (POM) and nanocomposites containing POSS's with different organic functional groups ePOSS, vPOSS and hPOSS (0.5% and 1% by weight). The nucleation effectiveness was assessed by DSC determination of crystallization temperature and by optical measurement of nucleation density and spherulites dimensions. An increase of crystallization temperature alone with a decrease of the average spherulites dimension deliver a proof of a nucleation - like activity of hPOSS. An additionally effect observed for POPSS modified POM was a higher homogeneity of the morphology.

  8. Interpenetrating polymer networks based on a thermoplastic elastomer, using radiation techniques

    NASA Astrophysics Data System (ADS)

    Shirodkar, Bhavna D.; Burford, Robert P.

    2001-07-01

    Styrene-butadiene-styrene thermoplastic elastomers can be transformed into Interpenetrating polymer networks using γ-radiation crosslinking. Trimethylol propanetriacrylate was used as the radiation crosslinker for styrene. The study shows that the hardness of the sample increased with radiation dose while the tensile strength remained constant.

  9. Modeling fiber Bragg grating device networks in photomechanical polymer optical fibers

    NASA Astrophysics Data System (ADS)

    Lanska, Joseph T.; Kuzyk, Mark G.; Sullivan, Dennis M.

    2015-09-01

    We report on the modeling of fiber Bragg grating (FBG) networks in poly(methyl methacrylate) (PMMA) polymer fibers doped with azo dyes. Our target is the development of Photomechanical Optical Devices (PODs), comprised of two FBGs in series, separated by a Fabry-Perot cavity of photomechanical material. PODs exhibit photomechanical multi-stability, with the capacity to access multiple length states for a fixed input intensity when a mechanical shock is applied. Using finite-difference time-domain (FDTD) numerical methods, we modeled the photomechanical response of both Fabry-Perot and Bragg-type PODs in a single polymer optical fiber. The polymer fiber was modeled as an instantaneous Kerr-type nonlinear χ(3) material. Our model correctly predicts the essential optical features of FBGs as well as the photomechanical multi-stability of nonlinear Fabry-Perot cavity-based PODs. Networks of PODs may provide a framework for smart shape-shifting materials and fast optical computation where the decision process is distributed over the entire network. In addition, a POD can act as memory, and its response can depend on input history. Our models inform and will accelerate targeted development of novel Bragg grating-based polymer fiber device networks for a variety of applications in optical computing and smart materials.

  10. Biodegradable Photo-Crosslinked Thin Polymer Networks Based on Vegetable Oil Hydroxyfatty Acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Novel crosslinked thin polymer networks based on vegetable oil hydroxyfatty acids (HFAs) were prepared by UV photopolymerization and their mechanical properties were evaluated. Two raw materials, castor oil and 7,10-dihydroxy-8(E)-octadecenoic acid (DOD) were used as sources of mono- and di-HFAs, r...

  11. Soft nanoparticles: Nano ionic networks of associated ionic polymers

    DOE PAGES

    Aryal, Dipak; Grest, Gary S.; Perahia, Dvora

    2016-12-09

    Directing the formation of nanostructures that serve as building blocks of membranes presents an immense step towards engineering controlled polymeric ion transport systems. Here, using the exquisite atomic detail captured by molecular dynamics simulations, we follow the assembly of a co-polymer that consists of polystyrene sulfonate tethered symmetrically to hydrophobic blocks, realizing a new type of long lived solvent-responsive soft nanoparticle.

  12. Soft nanoparticles: nano ionic networks of associated ionic polymers

    SciTech Connect

    Aryal, Dipak; Grest, Gary S.; Perahia, Dvora

    2017-01-01

    Directing the formation of nanostructures that serve as building blocks of membranes presents an immense step towards engineering controlled polymeric ion transport systems. Here, using the exquisite atomic detail captured by molecular dynamics simulations, we follow the assembly of a co-polymer that consists of polystyrene sulfonate tethered symmetrically to hydrophobic blocks, realizing a new type of long lived solvent-responsive soft nanoparticle.

  13. Structure–property relationships in hybrid dental nanocomposite resins containing monofunctional and multifunctional polyhedral oligomeric silsesquioxanes

    PubMed Central

    Wang, Weiguo; Sun, Xiang; Huang, Li; Gao, Yu; Ban, Jinghao; Shen, Lijuan; Chen, Jihua

    2014-01-01

    Organic-inorganic hybrid materials, such as polyhedral oligomeric silsesquioxanes (POSS), have the potential to improve the mechanical properties of the methacrylate-based composites and resins used in dentistry. In this article, nanocomposites of methacryl isobutyl POSS (MI-POSS [bears only one methacrylate functional group]) and methacryl POSS (MA-POSS [bears eight methacrylate functional groups]) were investigated to determine the effect of structures on the properties of dental resin. The structures of the POSS-containing networks were determined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. Monofunctional POSS showed a strong tendency toward aggregation and crystallization, while multifunctional POSS showed higher miscibility with the dimethacrylate monomer. The mechanical properties and wear resistance decreased with increasing amounts of MI-POSS, indicating that the MI-POSS agglomerates act as the mechanical weak point in the dental resins. The addition of small amounts of MA-POSS improved the mechanical and shrinkage properties. However, samples with a higher MA-POSS concentration showed lower flexural strength and flexural modulus, indicating that there is a limited range in which the reinforcement properties of MA-POSS can operate. This concentration dependence is attributed to phase separation at higher concentrations of POSS, which affects the structural integrity, and thus, the mechanical and shrinkage properties of the dental resin. Our results show that resin with 3% MA-POSS is a potential candidate for resin-based dental materials. PMID:24550674

  14. Nanometer-scale fabrication of hydrogen silsesquioxane (HSQ) films with post exposure baking.

    PubMed

    Kim, Dong-Hyun; Kang, Se-Koo; Yeom, Geun-Young; Jang, Jae-Hyung

    2013-03-01

    A nanometer-scale grating structure with a 60-nm-wide gap and 200-nm-wide ridge has been successfully demonstrated on a silicon-on-insulator substrate by using a 220-nm-thick hydrogen silsesquioxane (HSQ) negative tone electron beam resist. A post exposure baking (PEB) process and hot development process with low concentration (3.5 wt%) of tetramethylammonium hydroxide (TMAH) solution were introduced to realize the grating pattern. To study the effects of post exposure baking on the HSQ resist, Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses were carried out. From the FT-IR and XPS analyses, it was verified that a thin SiO2 with high cross-linked network structure was formed on the HSQ surface during the PEB step. This SiO2 layer prevents the formation of unwanted bonds on the HSQ surface, which results in clearly defined grating structures with a 60-nm-gap and 200-nm-wide-ridge on the 220-nm-thick HSQ resist. The nanometer-scale grating pattern was successfully transfered to the 280-nm-thick silicon layer of a silicon-on-insulator (SOI) substrate by using inductively-coupled-plasma-reactive-ion-etching (ICP-RIE).

  15. Thermoreversible associating polymer networks. I. Interplay of thermodynamics, chemical kinetics, and polymer physics.

    PubMed

    Hoy, Robert S; Fredrickson, Glenn H

    2009-12-14

    Hybrid molecular dynamics/Monte Carlo simulations are used to study melts of unentangled, thermoreversibly associating supramolecular polymers. In this first of a series of papers, we describe and validate a model that is effective in separating the effects of thermodynamics and chemical kinetics on the dynamics and mechanics of these systems, and is extensible to arbitrarily nonequilibrium situations and nonlinear mechanical properties. We examine the model's quiescent (and heterogeneous) dynamics, nonequilibrium chemical dynamics, and mechanical properties. Many of our results may be understood in terms of the crossover from diffusion-limited to kinetically limited sticky bond recombination, which both influences and is influenced by polymer physics, i.e., the connectivity of the parent chains.

  16. Pore Network Modeling of Multiphase Transport in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

    NASA Astrophysics Data System (ADS)

    Fazeli, Mohammadreza

    In this thesis, pore network modeling was used to study how the microstructure of the polymer electrolyte membrane (PEM) fuel cell gas diffusion layer (GDL) influences multiphase transport within the composite layer. An equivalent pore network of a GDL was used to study the effects of GDL/catalyst layer condensation points and contact quality on the spatial distribution of liquid water in the GDL. Next, pore networks extracted from synchrotron-based micro-computed tomography images of compressed GDLs were employed to simulate liquid water transport in GDL materials over a range of compression pressures, and favorable GDL compression values for preferred liquid water distributions were found for two commercially available GDL materials. Finally, a technique was developed for calculating the oxygen diffusivity in carbon paper substrates with a microporous layer (MPL) coating through pore network modeling. A hybrid network was incorporated into the pore network model, and effective diffusivity predictions of MPL coated GDL materials were obtained.

  17. Networked calix[4]arene polymers with unusual mechanical properties.

    PubMed

    Grima, Joseph N; Williams, Jennifer J; Evans, Kenneth E

    2005-08-28

    Polymeric networks built from calix[4]arenes that form a three dimensional folded structure have been predicted to exhibit negative Poisson's ratios (auxetic), an unusual property which makes them superior to conventional materials in many practical applications.

  18. Molecular dynamics simulations of highly cross-linked polymer networks: prediction of thermal and mechanical properties

    NASA Astrophysics Data System (ADS)

    Shenogina, Natalia; Tsige, Mesfin; Mukhopadhyay, Sharmila; Patnaik, Soumya

    2012-02-01

    We use all-atom molecular dynamics (MD) simulations to predict the mechanical and thermal properties of thermosetting polymers. Atomistic simulation is a promising tool which can provide detailed structure-property relationships of densely cross-linked polymer networks. In this work we study the thermo-mechanical properties of thermosetting polymers based on amine curing agents and epoxy resins and have focused on the DGEBA/DETDA epoxy system. At first we describe the modeling approach to construction of realistic all-atom models of densely cross-linked polymer matrices. Subsequently, a series of atomistic simulations was carried out to examine the simulation cell size effect as well as the role of cross-linking density and chain length of the resin strands on thermo-mechanical properties at different temperatures. Two different methods were used to deform the polymer networks. Both static and dynamic approaches to calculating the mechanical properties were considered and the thermo-mechanical properties obtained from our simulations were found in reasonable agreement with experimental values.

  19. Effects of molecular architecture on fluid ingress behavior of glassy polymer networks

    NASA Astrophysics Data System (ADS)

    Jaskson, Matthew Blaine

    This manuscript demonstrates the synthesis of glassy polymer network isomers to control morphological variations and study solvent ingress behavior independent of chemical affinity. Well-controlled network architectures with varying free volume average hole-sizes have been shown to substantially influence solvent ingress within glassy polymer networks. Bisphenol-A diglycidyl ether (DGEBA), bisphenol-F diglycidyl ether (DGEBF), Triglycidyl p-aminophenol (pAP, MY0510), Triglycidyl maminophenol (mAP, MY0610), and tetraglydicyl-4,4'-diamino-diphenyl methane (TGDDM, MY721) were cured with 3,3'- and 4,4'-diaminodiphenyl sulfone (DDS) at a stoichiometric ratio of 1:1 oxirane to amine active hydrogen to generate a series of network architectures with an average free volume hole-size (Vh) ranging between 54-82 A3. Polymer networks were exposed to water and a broad range of organic solvents ranging in van der Waals (vdW) volumes from 18-88 A3 for up to 10,000h time. A clear relationship between glassy polymer network Vh and fluid penetration has been established. As penetrant vdW volume approached Vh, uptake kinetics significantly decreased, and as penetrant vdW volume exceeded Vh, a blocking mechanism dominated ingress and prevented penetrant transport. These results suggest that reducing the free volume hole-size is a reasonable approach to control solvent properties for glassy polymer networks. New techniques to monitor and predict the diffusion behavior of liquids through glassy networks are also presented. Digital Image Correlation (DIC) was employed to accurately measure the strain developed during case II diffusion. This technique also presented a new theory for a relationship between sample topology and irreversible macroscopic brittle failure induced by solvent absorption. A new modeling technique has been developed which can accurately predict the chemical and physical interactions a solvent may have with a glassy network. This new model can be used as a

  20. Pt-Free Counter Electrodes with Carbon Black and 3D Network Epoxy Polymer Composites

    NASA Astrophysics Data System (ADS)

    Kang, Gyeongho; Choi, Jongmin; Park, Taiho

    2016-03-01

    Carbon black (CB) and a 3D network epoxy polymer composite, representing dual functions for conductive corrosion protective layer (CCPL) and catalytic layer (CL) by the control of CB weight ratio against polymer is developed. Our strategy provides a proper approach which applies high catalytic ability and chemical stability of CB in corrosive triiodide/iodide (I3-/I-) redox electrolyte system. The CB and a 3D network epoxy polymer composite coated on the stainless steel (SS) electrode to alternate counter electrodes in dye sensitized solar cells (DSSCs). A two-step spray pyrolysis process is used to apply a solution containing epoxy monomers and a polyfunctional amine hardener with 6 wt% CB to a SS substrate, which forms a CCPL. Subsequently, an 86 wt% CB is applied to form a CL. The excellent catalytic properties and corrosion protective properties of the CB and 3D network epoxy polymer composites produce efficient counter electrodes that can replace fluorine-doped tin oxide (FTO) with CCPL/SS and Pt/FTO with CL/CCPL/SS in DSSCs. This approach provides a promising approach to the development of efficient, stable, and cheap solar cells, paving the way for large-scale commercialization.

  1. Pt-Free Counter Electrodes with Carbon Black and 3D Network Epoxy Polymer Composites

    PubMed Central

    Kang, Gyeongho; Choi, Jongmin; Park, Taiho

    2016-01-01

    Carbon black (CB) and a 3D network epoxy polymer composite, representing dual functions for conductive corrosion protective layer (CCPL) and catalytic layer (CL) by the control of CB weight ratio against polymer is developed. Our strategy provides a proper approach which applies high catalytic ability and chemical stability of CB in corrosive triiodide/iodide (I3−/I−) redox electrolyte system. The CB and a 3D network epoxy polymer composite coated on the stainless steel (SS) electrode to alternate counter electrodes in dye sensitized solar cells (DSSCs). A two-step spray pyrolysis process is used to apply a solution containing epoxy monomers and a polyfunctional amine hardener with 6 wt% CB to a SS substrate, which forms a CCPL. Subsequently, an 86 wt% CB is applied to form a CL. The excellent catalytic properties and corrosion protective properties of the CB and 3D network epoxy polymer composites produce efficient counter electrodes that can replace fluorine-doped tin oxide (FTO) with CCPL/SS and Pt/FTO with CL/CCPL/SS in DSSCs. This approach provides a promising approach to the development of efficient, stable, and cheap solar cells, paving the way for large-scale commercialization. PMID:26961256

  2. Photopatterned collagen-hyaluronic acid interpenetrating polymer network hydrogels.

    PubMed

    Suri, Shalu; Schmidt, Christine E

    2009-09-01

    To engineer complex tissues, it is necessary to create hybrid scaffolds with micropatterned structural and biomechanical properties, which can closely mimic the intricate body tissues. The current report describes the synthesis of a novel photocrosslinkable interpenetrating polymeric network (IPN) of collagen and hyaluronic acid (HA) with precisely controlled structural and biomechanical properties. Both collagen and HA are present in crosslinked form in IPNs, and the two networks are entangled with each other. IPNs were also compared with semi-IPNs (SIPN), in which only collagen was in network form and HA chains were entangled in the collagen network without being photocrosslinked. Scanning electron microscopy images revealed that IPNs are denser than SIPNs, which results in their molecular reinforcement. This was further confirmed by rheological experiments. Because of the presence of the HA crosslinked network, the storage modulus of IPNs was almost two orders of magnitude higher than SIPNs. The degradation of the collagen-HA IPNs was slower than the SIPNs because of the presence of the crosslinked HA network. Increasing concentration of HA further altered the properties among IPNs. Cytocompatibility of IPNs was confirmed by Schwann cell and dermal fibroblasts adhesion and proliferation studies. We also fabricated patterned scaffolds with regions of IPNs and SIPNs within a bulk hydrogel, resulting in zonal distribution of crosslinking densities, viscoelasticities, water content and pore sizes at the micro- and macro-scales. With the ability to fine-tune the scaffold properties by performing structural modifications and to create patterned scaffolds, these hydrogels can be employed as potential candidates for regenerative medicine applications.

  3. Effect of Network Structure/Topology on Mechanical Properties of Crosslinked Polymers

    NASA Astrophysics Data System (ADS)

    Sharifi, Majid

    The interest in epoxy thermosetting polymers is widespread (e.g. Boeing 787 Dreamliner, windmill blades, automobiles, coatings, adhesives, etc.), and a demand still exists for improving toughness of these materials without degrading advantageous properties such as strength, modulus, and Tg. This study introduces novel approaches for improving the intrinsic mechanical characteristics of these polymers. The designed synthetic techniques focus on developing polymer materials with the same overall compositions but varying in network topologies, with distinct topological features in the size range of 5-50 nm, measured by SAXS and SEM. It was found that without altering chemical structure, the network topology of a dense thermoset can be engineered such that, under mechanical deformation, nano-cavities open and dissipate energy before rupturing covalent bonds, producing a tougher material without sacrificing strength, modulus, and even glass transition temperature. Modified structures also revealed higher resistance to fracture than the corresponding control structures. The major fracture mechanism responsible for the increased energy dissipation was found to be nano-cavitation. SEM images from the fracture surfaces showed clear cavities on the modified samples whereas none were seen on the fracture surface of the control samples. Overall, it was demonstrated that network topology can be used to tailor thermal and mechanical properties of thermosetting polymers. The experimental methodologies in this dissertation can directly and economically be applied to design polymeric materials with improved properties for desired applications. Although topology-based toughening was investigated on epoxy-amine polymers, the concept can be extended to most thermoset chemistries and perhaps to other brittle network forming materials.

  4. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  5. Strain-dependent characterization of electrode and polymer network of electrically activated polymer actuators

    NASA Astrophysics Data System (ADS)

    Töpper, Tino; Osmani, Bekim; Weiss, Florian M.; Winterhalter, Carla; Wohlfender, Fabian; Leung, Vanessa; Müller, Bert

    2015-04-01

    Fecal incontinence describes the involuntary loss of bowel content and affects about 45 % of retirement home residents and overall more than 12 % of the adult population. Artificial sphincter implants for treating incontinence are currently based on mechanical systems with failure rates resulting in revision after three to five years. To overcome this drawback, artificial muscle sphincters based on bio-mimetic electro-active polymer (EAP) actuators are under development. Such implants require polymer films that are nanometer-thin, allowing actuation below 24 V, and electrodes that are stretchable, remaining conductive at strains of about 10 %. Strain-dependent resistivity measurements reveal an enhanced conductivity of 10 nm compared to 30 nm sputtered Au on silicone for strains higher than 5 %. Thus, strain-dependent morphology characterization with optical microscopy and atomic force microscopy could demonstrate these phenomena. Cantilever bending measurements are utilized to determine elastic/viscoelastic properties of the EAP films as well as their long-term actuation behavior. Controlling these properties enables the adjustment of growth parameters of nanometer-thin EAP actuators.

  6. Preparation and characterization of aqueous polyurethane oil/polyacrylate latex interpenetrating polymer network

    NASA Astrophysics Data System (ADS)

    Zhou, M. M.; Ma, L. L.; Du, J.; Cao, F.; Xiao, J. J.

    2015-07-01

    A series of aqueous polyurethane oil (network I)/polyacrylate (network II) latex interpenetrating polymer networks (LIPNs) were synthesized via the technology of latex interpenetrating polymer network combined seed emulsion polymerization process. Fourier transform infrared (FTIR) spectroscopy, laser particle size distributing analyzer and universal tension machine were utilized to characterize the bulk structures and mechanical properties of LIPNs. For used as damping material, the damping performance of LIPNs were analyzed by dynamic mechanical analysis (DMA). It was found that the damping temperature region of LIPN was wider than those of aqueous polyurethane oil, the temperature region with greater tanδ changed with the TPGDA content and hard-/soft-segment mass weight ratio (mMMA/mBA) and the glass transition temperature (Tg) of the network I and network II in LIPN occurred within shift each other, even overlap with increasing mMMA/mBA value. The results show that LIPNs synthesized through the combined process have greater tanδ and wider damping temperature region, which is suitable for the use of damping coatings.

  7. Conductivity and properties of polysiloxane-polyether cluster-LiTFSI networks as hybrid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Boaretto, Nicola; Joost, Christine; Seyfried, Mona; Vezzù, Keti; Di Noto, Vito

    2016-09-01

    This report describes the synthesis and the properties of a series of polymer electrolytes, composed of a hybrid inorganic-organic matrix doped with LiTFSI. The matrix is based on ring-like oligo-siloxane clusters, bearing pendant, partially cross-linked, polyether chains. The dependency of the thermo-mechanic and of the transport properties on several structural parameters, such as polyether chains' length, cross-linkers' concentration, and salt concentration is studied. Altogether, the materials show good thermo-mechanical and electrochemical stabilities, with conductivities reaching, at best, 8·10-5 S cm-1 at 30 °C. In conclusion, the cell performances of one representative sample are shown. The scope of this report is to analyze the correlations between structure and properties in networked and hybrid polymer electrolytes. This could help the design of optimized polymer electrolytes for application in lithium metal batteries.

  8. Field-effect Flow Control in Polymer Microchannel Networks

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  10. Quantitative prediction of imprinting factor of molecularly imprinted polymers by artificial neural network

    NASA Astrophysics Data System (ADS)

    Nantasenamat, Chanin; Naenna, Thanakorn; Ayudhya, Chartchalerm Isarankura Na; Prachayasittikul, Virapong

    2005-07-01

    Artificial neural network (ANN) implementing the back-propagation algorithm was applied for the calculation of the imprinting factors (IF) of molecularly imprinted polymers (MIP) as a function of the computed molecular descriptors of template and functional monomer molecules and mobile phase descriptors. The dataset used in our study were obtained from the literature and classified into two distinctive datasets on the basis of the polymer's morphology, irregularly sized MIP and uniformly sized MIP datasets. Results revealed that artificial neural network was able to perform well on datasets derived from uniformly sized MIP ( n=23, r=0.946, RMS=2.944) while performing poorly on datasets derived from irregularly sized MIP ( n=75, r=0.382, RMS=6.123). The superior performance of the uniformly sized MIP dataset over the irregularly sized MIP dataset could be attributed to its more predictable nature owing to the consistency of MIP particles, uniform number and association constant of binding sites, and minimal deviation of the imprinted polymers. The ability to predict the imprinting factor of imprinted polymer prior to performing actual experimental work provide great insights on the feasibility of the interaction between template-functional monomer pairs.

  11. Porous Polymer Networks: Synthesis, Porosity, and Applications in Gas Storage/Separation

    SciTech Connect

    Lu, Weigang; Yuan, Daqiang; Zhao, Dan; Schilling, Christine Inge; Plietzsch, Oliver; Muller, Thierry; Braese, Stefano; Guenther, Johannes; Blumel, Janet; Krishna, Rajamani; Li, Zhen; Zhou, Hong-Cai

    2010-11-09

    Three porous polymer networks (PPNs) have been synthesized by the homocoupling of tetrahedral monomers. Like other hyper-cross-linked polymer networks, these materials are insoluble in conventional solvents and exhibit high thermal and chemical stability. Their porosity was confirmed by N₂ sorption isotherms at 77 K. One of these materials, PPN-3, has a Langmuir surface area of 5323 m² g-1. Their clean energy applications, especially in H₂, CH₄, and CO₂ storage, as well as CO₂/CH₄ separation, have been carefully investigated. Although PPN-1 has the highest gas affinity because of its smaller pore size, the maximal gas uptake capacity is directly proportional to their surface area. PPN-3 has the highest H₂ uptake capacity among these three (4.28 wt %, 77 K). Although possessing the lowest surface area, PPN-1 shows the best CO₂/CH₄ selectivity among them.

  12. Porphyrin network polymers prepared via a click reaction and facilitated oxygen permeation through their membranes.

    PubMed

    Chikushi, Natsuru; Ohara, Emiko; Hisama, Ayako; Nishide, Hiroyuki

    2014-05-01

    Network polymers of cobaltporphyrin derivatives are prepared by a facile click reaction via the Michael addition of acetoacetate-substituted tetraphenyl cobaltporphyrin and tri- or tetra-acrylates. The conversion is saturated for 1 h in the presence of a catalyst, which almost reaches the same gelation point of the formed network polymers. Deeply and homogeneously red-colored membranes with a sub-micrometer thickness are yielded on a porous supporting membrane. They are still tough even with a very high content of the rigid porphyrin residue. The oxygen permeability is high, at 10-100 Barrer, and the oxygen/nitrogen permselectivity (PO2/PN2) is significantly enhanced with the porphyrin content reaching 30, for the membranes with ca. 70 wt% porphyrin content.

  13. From pico to nano: biofunctionalization of cube-octameric silsesquioxanes by peptides and miniproteins.

    PubMed

    Fabritz, Sebastian; Hörner, Sebastian; Könning, Doreen; Empting, Martin; Reinwarth, Michael; Dietz, Christian; Glotzbach, Bernhard; Frauendorf, Holm; Kolmar, Harald; Avrutina, Olga

    2012-08-21

    Polyhedral silsesquioxanes are considered valuable conjugation scaffolds. Nevertheless, only a few examples of silsesquioxane-assembled peptide oligomers have been reported to date. We developed a new bioorthogonal cube-octameric silsesquioxane (COSS) scaffold bearing eight aminooxy coupling sites allowing for the conjugation of diverse peptides via oxime ligation. We found that the coupling efficacy depends on the ligand in view of steric hindrance and electrostatic repulsion. For the first time scaffold-based conjugation of cystine-knot miniproteins having a backbone of about thirty amino acids was successfully accomplished without loss of bioactivity. Atomic force microscopy (AFM) provided further knowledge on the size of COSS verifying them as picoscaffolds growing upon bioconjugation to nano-dimension.

  14. Facile one-pot synthesis of porphyrin based porous polymer networks (PPNs) as biomimetic catalysts

    SciTech Connect

    Zou, LF; Feng, DW; Liu, TF; Chen, YP; Fordham, S; Yuan, S; Tian, J; Zhou, HC

    2015-01-01

    Stable porphyrin based porous polymer networks, PPN-23 and PPN-24, have been synthesized through a facile one-pot approach by the aromatic substitution reactions of pyrrole and aldehydes. PPN-24(Fe) shows high catalytic efficiency as a biomimetic catalyst in the oxidation reaction of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2.

  15. Synthesis and Characterization of Conducting Elastomers Based on Interpenetrated C60-Derived Polymer Networks

    DTIC Science & Technology

    2007-11-02

    CHARACTERIZATION OF CONDUCTING ELASTOMERS BASED ON INTERPENETRATED C 60-DERIVED POLYMER NETWORKS" 6. AUTHOR( S ) PROFESSOR LONG Y. CHIANG PROFESSOR LEE Y. WANG 7...PERFORMING ORGANIZATION NAME( S ) AND ADDRESS(ES) IHE FOUNDATION OF CONDENSED MATTER SCIENCES NATIONAL TAIWAN UNIVERSITY 1 ROOSEVELT ROAD TAIPEI...TAIWAN 9. SPONSORING/MONITORING AGENCY NAME( S ) AND ADDRESS(ES) ASIAN OFFICE OF AEROSPACE RESEARCH AND DEVELOPMENT (AOARD) UNIT 45002 f\\P0 AP 96337

  16. Polymer-assisted direct deposition of uniform carbon nanotube bundle networks for high performance transparent electrodes.

    PubMed

    Hellstrom, Sondra L; Lee, Hang Woo; Bao, Zhenan

    2009-06-23

    Flexible transparent electrodes are crucial for touch screen, flat panel display, and solar cell technologies. While carbon nanotube network electrodes show promise, characteristically poor dispersion properties have limited their practicality. We report that addition of small amounts of conjugated polymer to nanotube dispersions enables straightforward fabrication of uniform network electrodes by spin-coating and simultaneous tuning of parameters such as bundle size and density. After treatment in thionyl chloride, electrodes have sheet resistances competitive with other reported carbon nanotube based transparent electrodes to date.

  17. Polymer Networks Produced by Marine Diatoms in the Northern Adriatic Sea

    PubMed Central

    Svetličić, Vesna; Žutić, Vera; Radić, Tea Mišić; Pletikapić, Galja; Zimmermann, Amela Hozić; Urbani, Ranieri

    2011-01-01

    Using high resolution molecular technique of atomic force microscopy, we address the extracellular polymer production of Adriatic diatom Cylindrotheca closterium analyzed at the single cell level and the supramolecular organization of gel phase isolated from the Northern Adriatic macroaggregates. Our results revealed that extracellular polysaccharides freshly produced by marine diatoms can self-assemble directly to form gel network characteristics of the macroscopic gel phase in the natural aquatorium. Based on the experiments performed with isolated polysaccharide fractions of C. closterium and of macroaggregates gel phase, we demonstrated that the polysaccharide self-assembly into gel network can proceed independent of any bacterial mediation or interaction with inorganic particles. PMID:21731556

  18. Stability in alkaline aqueous electrolyte of air electrode protected with fluorinated interpenetrating polymer network membrane

    NASA Astrophysics Data System (ADS)

    Bertolotti, Bruno; Messaoudi, Houssam; Chikh, Linda; Vancaeyzeele, Cédric; Alfonsi, Séverine; Fichet, Odile

    2015-01-01

    We developed original anion exchange membranes to protect air electrodes operating in aqueous lithium-air battery configuration, i.e. supplied with atmospheric air and in concentrated aqueous lithium hydroxide. These protective membranes have an interpenetrating polymer network (IPN) architecture combining a hydrogenated cationic polyelectrolyte network based on poly(epichlorohydrin) (PECH) and a fluorinated neutral network based on perfluoropolyether (Fluorolink® MD700). Two phases, each one rich in one of the polymer, are co-continuous in the materials. This morphology allows combining their properties according to the weight proportions of each polymer. Thus, PECH/Fluorolink IPNs show ionic conductivity varying from 1 to 2 mS cm-1, water uptake from 30 to 90 wt.% and anionic transport number from 0.65 to 0.80 when the PECH proportion varies from 40 to 90 wt.%. These membranes have been systematically assembled on air electrodes. Air electrode protected with PECH/Fluorolink 70/30 IPN shows outstanding stability higher than 1000 h, i.e. a 20-fold increase in the lifetime of the non-modified electrode. This efficient membrane/air electrode assembly is promising for development of alkaline electrolyte based storage or production energy systems, such as metal air batteries or alkaline fuel cells.

  19. Ionically Cross-Linked Polymer Networks for the Multiple-Month Release of Small Molecules

    PubMed Central

    2016-01-01

    Long-term (multiple-week or -month) release of small, water-soluble molecules from hydrogels remains a significant pharmaceutical challenge, which is typically overcome at the expense of more-complicated drug carrier designs. Such approaches are payload-specific and include covalent conjugation of drugs to base materials or incorporation of micro- and nanoparticles. As a simpler alternative, here we report a mild and simple method for achieving multiple-month release of small molecules from gel-like polymer networks. Densely cross-linked matrices were prepared through ionotropic gelation of poly(allylamine hydrochloride) (PAH) with either pyrophosphate (PPi) or tripolyphosphate (TPP), all of which are commonly available commercial molecules. The loading of model small molecules (Fast Green FCF and Rhodamine B dyes) within these polymer networks increases with the payload/network binding strength and with the PAH and payload concentrations used during encapsulation. Once loaded into the PAH/PPi and PAH/TPP ionic networks, only a few percent of the payload is released over multiple months. This extended release is achieved regardless of the payload/network binding strength and likely reflects the small hydrodynamic mesh size within the gel-like matrices. Furthermore, the PAH/TPP networks show promising in vitro cytocompatibility with model cells (human dermal fibroblasts), though slight cytotoxic effects were exhibited by the PAH/PPi networks. Taken together, the above findings suggest that PAH/PPi and (especially) PAH/TPP networks might be attractive materials for the multiple-month delivery of drugs and other active molecules (e.g., fragrances or disinfectants). PMID:26811936

  20. Octa, deca, and dodeca(4-nitrophenyl) cage silsesquioxanes via 4-trimethylsilylphenyl derivatives.

    PubMed

    Miyazato, Akio; Pakjamsai, Chitsakon; Kawakami, Yusuke

    2010-04-07

    Pure octa, deca, and dodeca(4-nitrophenyl) cage silsesquioxanes were obtained by regio-selective 4-nitration of octa, deca, and dodeca(4-trimethylsilylphenyl) cage silsesquioxanes via ipso-substitution of trimethylsilyl-phenyl bonds by fuming nitric acid. 3-Nitration of octa(4-methylphenyl)octasilesquioxane was also described. The starting octa(4-methyl-, 4-isopropyl- and 4-trimethylsilylphenyl)octasilsesquioxanes were selectively formed in 9-21% isolated yield in the presence of hydrochloric acid. Mixtures of octa, deca and dodecasilsesquioxanes, with decasilsesquioxane as the main component, were formed in the presence of tetrabutylammmonium fluoride as a catalyst. All the cage compounds could be separated mainly by crystallization.

  1. Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.

    PubMed

    Rapakousiou, Amalia; Deraedt, Christophe; Irigoyen, Joseba; Wang, Yanlan; Pinaud, Noël; Salmon, Lionel; Ruiz, Jaime; Moya, Sergio; Astruc, Didier

    2015-03-02

    The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

  2. Synthesis and characterization of complex polymer architectures

    NASA Astrophysics Data System (ADS)

    Farmer, Brandon Scott

    Anionic polymerization based upon high vacuum technique has been used to synthesize different star polymers using varying linking techniques. In particular chlorosilanes, divinylbenzene, and polyhedral oligomeric silsesquioxane (POSS) chlorosilane derivatives were used in the synthesis of star polymers. These polymers, along with polymers synthesized by others, have been characterized by a range of methods in this work. A series of polyisoprene (PI) stars were synthesized from dimethylaminopropyllithium (DMAPLi) and subsequently hydrogenated to form poly (ethylene-co-propylene) (PEP) these were characterized by size exclusion chromatography (SEC) coupled with online two angle laser light scattering (TALLS). These polymers were synthesized in an attempt to make a new series of viscosity index improvers as an oil additive. The polymers were characterized by differential scanning calorimetry and thermal gravimetric analysis. A novel process for producing eight arm star polymers was explored using a Polyhedral Oligomeric Silsesquioxane (POSS) modified with chlorosilanes as the linking agent. The arms of these stars were prepared polybutadiene prepared anionically. A study of the effect of living end-groups was also explored by endcapping the living polybutadiene with a polystrylanion and the linking efficiency was monitored. These polymers were also characterized by SEC coupled with TALLS.

  3. Effect of crystals and fibrous network polymer additives on cellular morphology of microcellular foams

    NASA Astrophysics Data System (ADS)

    Miyamoto, Ryoma; Utano, Tatsumi; Yasuhara, Shunya; Ishihara, Shota; Ohshima, Masahiro

    2015-05-01

    In this study, the core-back foam injection molding was used for preparing microcelluar polypropylene (PP) foam with either a 1,3:2,4 bis-O-(4-methylbenzylidene)-D-sorbitol gelling agent (Gel-all MD) or a fibros network polymer additive (Metablen 3000). Both agent and addiive could effectively control the celluar morphology in foams but somehow different ways. In course of cooling the polymer with Gel-all MD in the mold caity, the agent enhanced the crystal nucleation and resulted in the large number of small crystals. The crystals acted as effective bubble nucleation agent in foaming process. Thus, the agent reduced the cell size and increased the cell density, drastically. Furthermore, the small crystals provided an inhomogenuity to the expanding cell wall and produced the high open cell content with nano-scale fibril structure. Gell-all as well as Metablene 3000 formed a gel-like fibrous network in melt. The network increased the elongational viscosity and tended to prevent the cell wall from breaking up. The foaming temperature window was widened by the presence of the network. Especially, the temperature window where the macro-fibrous structure was formed was expanded to the higher temperature. The effects of crystal nucleating agent and PTFE on crystals' size and number, viscoelsticity, rheological propreties of PP and cellular morphology were compared and thorougly investigated.

  4. Modeling heterogeneous polymer-grafted nanoparticle networks having biomimetic core-shell structure

    NASA Astrophysics Data System (ADS)

    Mbanga, Badel L.; Yashin, Victor V.; Holten-Andersen, Niels; Balazs, Anna C.

    Inspired by the remarkable mechanical properties of such biological structures as mussel adhesive fibers, we use 3D computational modeling to study the behavior of heterogeneous polymer-grafted nanoparticle (PGN) networks under tensile deformation. The building block of a PGN network is a nanoparticle with grafted polymer chains whose free ends' reactive groups can form both permanent and labile bonds with the end chains on the nearby particles. The tunable behavior of cross-linked PGN networks makes them excellent candidates for designing novel materials with enhanced mechanical properties. Here, we consider the PGN networks having the core-shell structures, in which the type and strength of the inter-particle bonds in the outer shell differ from those in the core. Using the computer simulations, we obtain and compare the ultimate tensile properties (strength, toughness, ductility) and the strain recovery properties for the uniform samples and various core-shell structures. We demonstrate that the core-shell structures could be designed to obtain highly resilient self-healing materials

  5. Electron Microscopy Imaging of Single-Wall Carbon Nanotube Networks in Polymers

    NASA Astrophysics Data System (ADS)

    Jesse, Stephen; Guillorn, Michael; Ivanov, Ilia; Puretzky, Alex; Howe, Jane; Britt, Phillip; Geohegan, David

    2004-03-01

    Scanning electron microscopy (SEM) imaging techniques have been applied to study the electrical transport properties of conducting networks of single-walled carbon nanotubes (SWNTs) in insulating polymers. Two SEM techniques were used. One approach uses specimen current (SC) measurements to visualize current flow within the SWNT network. Another and novel approach is highly sensitive to electrical potential within the networks and occurs as a result of the large electric fields generated in the vicinity of the nanotube bundles. High-resolution transmission electron microscopy was used to characterize the SWNT bundles in the PMMA. These techniques permit a direct experimental approach to characterize and understand potential distribution and current flow through percolation networks formed by nanotube bundles in polymers, or more generally, nanorods or nanowires in various matrices. This research was sponsored by NASA-Langley Research Center and the Laboratory-Directed Research and Development Program at ORNL, and the U.S. Department of Energy under contract DE-AC05-00OR22725 with the Oak Ridge National Laboratory, managed by UT-Battelle, LLC.

  6. Structure and properties of polymer hydrogels based on interpenetration of a hydrophilic and a hydrophobic network

    NASA Astrophysics Data System (ADS)

    Gallego Ferrer, Gloria

    Synthetic polymer hydrogels have been proposed for many biomedical applications because of their good biocompatibility and water permeation properties, and the possibility of synthesizing materials with a broad spectrum of micromorphologies and specific properties. However, the low mechanical strength of hydrogels hinders many of their potential uses. New families of polymers have been developed, seeking to improve the mechanical behaviour of the corresponding hydrogels. For these purpose, in the present work sequential interpenetrating polymer networks (IPNs) with controllable degree of hydrophilicity have been prepared by polymerization of hydroxyethyl acrylate (HEA) monomer with different concentrations in ethanol inside a previously polymerized poly(ethyl acrylate) (PEA) network. These polymer hydrogels have been investigated as regards their morphology and their physical, thermodynamical, equilibrium water sorption, and water transport properties. The properties of these systems are correlated and compared with those measured on systems which share the same hydrophilic component, but differ in the morphology of the hydrophilic phase. The IPNs thus prepared are phase-separated systems in which two types of domains alternate (hydrophobic and hydrophilic). The hydrophilic character of the IPNs is governed by the PHEA component in them, which behaves in the same manner as would the pure polymer. A thermodynamic analysis of the PHEA hydrogel allowed to analyze the states of water in the PHEA hydrogel. The positive values of the specific mixing increment of the residual Gibbs free energy indicates that the affinity of water to mix with PHEA is of combinatorial nature, the interaction between water molecules and polymer chains is a labile interaction. The dependence on the water content of the Flory-Huggins interaction parameter was analyzed. The water content in the hydrogel for water activity equal to one is different when it is equilibrated in a medium of

  7. Carbon nanotube-based polymer nanocomposites: Fractal network to hierarchical morphology

    NASA Astrophysics Data System (ADS)

    Chatterjee, Tirtha

    The dispersion of anisotropic nanoparticles such as single-walled carbon nanotubes in polymeric matrices promises the ability to develop advanced materials with controlled and tailored combinations of properties. However, dispersion of such nanotubes in a polymer matrix is an extremely challenging task due to strong attractive interactions between the nanotubes. The successful dispersion of single-walled carbon nanotubes in poly(ethylene oxide) using an anionic surfactant (lithium dodecyl sulfate) as compatibilizer is reported here. The geometrical percolation threshold (pc, in vol %) of nanotubes, as revealed by melt-state rheological measurements, is found to be at ˜ 0.09 vol % loading, which corresponds to an effective tube anisotropy of ˜ 650. The system shows an even earlier development of the electrical percolation at 0.03 vol % SWNT loading as obtained by electrical conductivity measurements. In their quiescent state, the nanotubes show hierarchical fractal network (mass fractal dimension ˜ 2.3 +/- 0.2) made of aggregated flocs. Inside the floc, individual or small bundles of nanotubes overlap each other to form a dense mesh. The interfloc interactions provides the stress bearing capacity for these nano composites and are responsible for the unique modulus scaling of these systems (˜(p-pc)delta, 3.0 ≤ delta ≤ 4.5). The interaction is inversely related to the particle dispersion state, which influences the absolute values of the viscoelastic parameters. As a direct consequence of the self-similar fractal network, the linear flow properties display 'time-temperature-composition' superposition. This superposability can be extended for non-linear deformations when the non-linear properties are scaled by the local strain experienced by the elements of the network. More interestingly, under steady shear, these nanocomposites show network-independent behavior. The absolute stress value is a function of the nanotube loading, but the characteristic time

  8. Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

    SciTech Connect

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G.; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S.; Do, Changwoo

    2016-07-19

    Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.

  9. Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

    DOE PAGES

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; ...

    2016-07-19

    Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less

  10. Multifunctional supramolecular polymer networks as next-generation consolidants for archaeological wood conservation.

    PubMed

    Walsh, Zarah; Janeček, Emma-Rose; Hodgkinson, James T; Sedlmair, Julia; Koutsioubas, Alexandros; Spring, David R; Welch, Martin; Hirschmugl, Carol J; Toprakcioglu, Chris; Nitschke, Jonathan R; Jones, Mark; Scherman, Oren A

    2014-12-16

    The preservation of our cultural heritage is of great importance to future generations. Despite this, significant problems have arisen with the conservation of waterlogged wooden artifacts. Three major issues facing conservators are structural instability on drying, biological degradation, and chemical degradation on account of Fe(3+)-catalyzed production of sulfuric and oxalic acid in the waterlogged timbers. Currently, no conservation treatment exists that effectively addresses all three issues simultaneously. A new conservation treatment is reported here based on a supramolecular polymer network constructed from natural polymers with dynamic cross-linking formed by a combination of both host-guest complexation and a strong siderophore pendant from a polymer backbone. Consequently, the proposed consolidant has the ability to chelate and trap iron while enhancing structural stability. The incorporation of antibacterial moieties through a dynamic covalent linkage into the network provides the material with improved biological resistance. Exploiting an environmentally compatible natural material with completely reversible chemistries is a safer, greener alternative to current strategies and may extend the lifetime of many culturally relevant waterlogged artifacts around the world.

  11. Multifunctional supramolecular polymer networks as next-generation consolidants for archaeological wood conservation

    PubMed Central

    Walsh, Zarah; Janeček, Emma-Rose; Hodgkinson, James T.; Sedlmair, Julia; Koutsioubas, Alexandros; Spring, David R.; Welch, Martin; Hirschmugl, Carol J.; Toprakcioglu, Chris; Nitschke, Jonathan R.; Jones, Mark; Scherman, Oren A.

    2014-01-01

    The preservation of our cultural heritage is of great importance to future generations. Despite this, significant problems have arisen with the conservation of waterlogged wooden artifacts. Three major issues facing conservators are structural instability on drying, biological degradation, and chemical degradation on account of Fe3+-catalyzed production of sulfuric and oxalic acid in the waterlogged timbers. Currently, no conservation treatment exists that effectively addresses all three issues simultaneously. A new conservation treatment is reported here based on a supramolecular polymer network constructed from natural polymers with dynamic cross-linking formed by a combination of both host-guest complexation and a strong siderophore pendant from a polymer backbone. Consequently, the proposed consolidant has the ability to chelate and trap iron while enhancing structural stability. The incorporation of antibacterial moieties through a dynamic covalent linkage into the network provides the material with improved biological resistance. Exploiting an environmentally compatible natural material with completely reversible chemistries is a safer, greener alternative to current strategies and may extend the lifetime of many culturally relevant waterlogged artifacts around the world. PMID:25385610

  12. Photomechanical bending mechanics of polydomain azobenzene liquid crystal polymer network films

    SciTech Connect

    Cheng Liang; Torres, Yanira; Oates, William S.; Lee, Kyung Min; McClung, Amber J.; Baur, Jeffery; White, Timothy J.

    2012-07-01

    Glassy, polydomain azobenzene liquid crystal polymer networks (azo-LCNs) have been synthesized, characterized, and modeled to understand composition dependence on large amplitude, bidirectional bending, and twisting deformation upon irradiation with linearly polarized blue-green (440-514 nm) light. These materials exhibit interesting properties for adaptive structure applications in which the shape of the photoresponsive material can be rapidly reconfigured with light. The basis for the photomechanical output observed in these materials is absorption of actinic light by azobenzene, which upon photoisomerization dictates an internal stress within the local polymer network. The photoinduced evolution of the underlying liquid crystal microstructure is manifested as macroscopic deformation of the glassy polymer film. Accordingly, this work examines the polarization-controlled bidirectional bending of highly concentrated azo-LCN materials and correlates the macroscopic output (observed as bending) to measured blocked stresses upon irradiation with blue-green light of varying polarization. The resulting photomechanical output is highly dependent on the concentration of crosslinked azobenzene mesogens employed in the formulation. Experiments that quantify photomechanical bending and photogenerated stress are compared to a large deformation photomechanical shell model to quantify the effect of polarized light interactions with the material during static and dynamic polarized light induced deformation. The model comparisons illustrate differences in internal photostrain and deformation rates as a function of composition and external mechanical constraints.

  13. Destruction and recovery of a nanorod conductive network in polymer nanocomposites via molecular dynamics simulation.

    PubMed

    Gao, Yangyang; Cao, Dapeng; Wu, Youping; Liu, Jun; Zhang, Liqun

    2016-03-28

    By adopting coarse-grained molecular dynamics simulation, we investigate the effects of end-functionalization and shear flow on the destruction and recovery of a nanorod conductive network in a functionalized polymer matrix. We find that the end-functionalization of polymeric chains can enhance the electrical conductivity of nanorod filled polymer nanocomposites, indicated by the decrease of the percolation threshold. However, there exists an optimal end-functionalization extent to reach the maximum electrical conductivity. In the case of steady shear flow, both homogeneous conductive probability and directional conductive probability perpendicular to the shear direction decrease with the shear rate, while the directional conductive probability parallel to the shear direction increases. Importantly, we develop a semi-empirical equation to describe the change of the homogeneous conductive probability as a function of the shear rate. Meanwhile, we obtain an empirical formula describing the relationship between the anisotropy of the conductive probability and the orientation of the nanorods. In addition, the conductivity stability increases with increasing nanorod volume fraction. During the recovery process of the nanorod conductive network, it can be fitted well by the model combining classical percolation theory and a time-dependent nanorod aggregation kinetic equation. The fitted recovery rate is similar for different nanorod volume fractions. In summary, this work provides some rational rules for fabricating polymer nanocomposites with excellent performance of electrical conductivity.

  14. A cracked polymer templated metal network as a transparent conducting electrode for ITO-free organic solar cells.

    PubMed

    Rao, K D M; Hunger, Christoph; Gupta, Ritu; Kulkarni, Giridhar U; Thelakkat, Mukundan

    2014-08-07

    We report a highly transparent, low resistance Ag metal network templated by a cracked polymer thin film and its incorporation in an organic solar cell. The performance of this scalable metallic network is comparable to that of conventional ITO electrodes. This is a general approach to replace ITO in diverse thin film devices.

  15. Using time-of-flight secondary ion mass spectrometry and multivariate statistical analysis to detect and image octabenzyl-polyhedral oligomeric silsesquioxane in polycarbonate

    NASA Astrophysics Data System (ADS)

    Smentkowski, V. S.; Duong, H. M.; Tamaki, R.; Keenan, M. R.; Ohlhausen, J. A. Tony; Kotula, P. G.

    2006-11-01

    Silsesquioxane, with an empirical formula of RSiO 3/2, has the potential to combine the mechanical properties of plastics with the oxidative stability of ceramics in one material [D.W. Scott, J. Am. Chem. Soc. 68 (1946) 356; K.J. Shea, D.A. Loy, Acc. Chem. Res. 34 (2001) 707; K.-M. Kim, D.-K. Keum, Y. Chujo, Macromolecules 36 (2003) 867; M.J. Abad, L. Barral, D.P. Fasce, R.J.J. William, Macromolecules 36 (2003) 3128]. The high sensitivity, surface specificity, and ability to detect and image high mass additives make time-of-flight secondary ion mass spectrometry (ToF-SIMS) a powerful surface analytical instrument for the characterization of polymer composite surfaces in an analytical laboratory [J.C. Vickerman, D. Briggs (Eds.), ToF-SIMS Surface Analysis by Mass Spectrometry, Surface Spectra/IMPublications, UK, 2001; X. Vanden Eynde, P. Bertand, Surf. Interface Anal. 27 (1999) 157; P.M. Thompson, Anal. Chem. 63 (1991) 2447; S.J. Simko, S.R. Bryan, D.P. Griffis, R.W. Murray, R.W. Linton, Anal. Chem. 57 (1985) 1198; S. Affrossman, S.A. O'Neill, M. Stamm, Macromolecules 31 (1998) 6280]. In this paper, we compare ToF-SIMS spectra of control samples with spectra generated from polymer nano-composites based on octabenzyl-polyhedral oligomeric silsesquioxane (BnPOSS) as well as spectra (and images) generated from multivariate statistical analysis (MVSA) of the entire spectral image. We will demonstrate that ToF-SIMS is able to detect and image low concentrations of BnPOSS in polycarbonate. We emphasize the use of MVSA tools for converting the massive amount of data contained in a ToF-SIMS spectral image into a smaller number of useful chemical components (spectra and images) that fully describe the ToF-SIMS measurement.

  16. MEMBRANE TECHNOLOGY: OPPORTUNITIES FOR POLYHEDRAL OLIGOMERIC SILSESQUIOXANES (POSS) IN MEMBRANE-BASED SEPARATIONS

    EPA Science Inventory

    Membrane Technology: Opportunities for Polyhedral Oligomeric Silsesquioxanes (POSS?) in Membrane-Based Separations

    Leland M. Vane, Ph.D.
    U.S. Environmental Protection Agency
    Office of Research & Development
    Cincinnati, OH 45268
    Vane.Leland@epa.gov

    A sign...

  17. Interpenetrating polymer network of locust bean gum-poly (vinyl alcohol) for controlled release drug delivery.

    PubMed

    Kaity, Santanu; Isaac, Jinu; Ghosh, Animesh

    2013-04-15

    A novel interpenetrating polymer network (IPN) microspheres of locust bean gum (LBG) and poly (vinyl alcohol) (PVA) was developed for oral controlled release of buflomedil hydrochloride (BH) by emulsion crosslinking method using glutaraldehyde as crosslinker. The effects of gum-polymer ratio, concentration of crosslinker and internal phase viscosity were evaluated thoroughly. Drug entrapment efficiency, particle size distribution, swelling property and in vitro release characteristics with kinetic modelling of microspheres were evaluated. The microspheres were characterised by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), solid state C(13) NMR, X-ray diffraction study (XRD) and differential scanning colorimetry (DSC). The microspheres showed control release property without showing any incompatibility in IPN device. Hence, IPN microspheres of LBG and PVA can be used as a potential carrier for controlled oral delivery of highly water soluble drugs like BH.

  18. Effects of disorder and chain stiffening on the elasticity of flexible polymer networks

    NASA Astrophysics Data System (ADS)

    Caroli, Christiane; Lemaître, Anaël

    2017-03-01

    We examine how the distribution of contour lengths and the high-stretch stiffening of individual chain segments affect the macroscopic shear modulus of flexible polymer gels, using a two-dimensional numerical model in which polymer segments form a triangular network and disorder is introduced by varying their contour lengths. We show that, in the relevant parameter range: (i) the nonaffine contribution to the shear modulus is negligible, i.e., the Born approximation is satisfactory, and (ii) the shear modulus is dominated by the contribution originating from equilibrium chain tensions. Moreover, mechanical equilibration at the nodes induces specific correlations between the end-to-end distances and contour lengths of chain segments, which must be properly accounted for to construct reasonable estimates of chain pressure and shear modulus.

  19. Radiation synthesis and characterisation of the network structure of natural/synthetic double-network superabsorbent polymers

    NASA Astrophysics Data System (ADS)

    Şen, Murat; Hayrabolulu, Hande

    2012-09-01

    In this study radiation synthesis and characterisation of the network structure of acrylic acid sodium salt/locust bean gum, (AAcNa/LBG) natural/synthetic double-network super absorbent polymers were investigated. Quartet systems composed of acrylic acid sodium salt/locust bean gum/N,N methylene bis acrylamide/water (AAcNa/LBG/MBAAm/water) were prepared at varying degree of neutralisations (DN) by controlling the DN value of AAc and irradiated with gamma rays at ambient temperature at a very low dose rate. The influences of the DN on the swelling and network properties were examined. It was observed that the DN strongly affected the gelation and super absorption properties of the gels. Molecular weight between crosslinks (M), effective crosslink density (νe) and mesh size (ξ) of SAPs were calculated from swelling and shear modules data obtained from compression and oscillatory frequency sweep tests. M values obtained from the uniaxial deformation experiments were very close to those obtained from the oscillatory shear experiments excluding the completely neutralised gel system. It was concluded that the uniaxial compression technique could be used for the characterisation of the network structure of a hydrogel as along with the rheological analyses; however, a very precise control of the gel size was also needed.

  20. Evaluation of Metal-Organic Frameworks and Porous Polymer Networks for CO2 -Capture Applications.

    PubMed

    Verdegaal, Wolfgang M; Wang, Kecheng; Sculley, Julian P; Wriedt, Mario; Zhou, Hong-Cai

    2016-03-21

    This manuscript presents experimental data for 20 adsorption materials (metal-organic frameworks, porous polymer networks, and Zeolite-5A), including CO2 and N2 isotherms and heat capacities. With input from only experimental data, working capacities per energy for each material were calculated. Furthermore, by running seven different carbon-capture scenarios in which the initial flue-gas composition and process temperature was systematically changed, we present a range of performances for each material and quantify how sensitive each is to these varying parameters. The presented calculations provide researchers with a tool to investigate promising carbon-capture materials more easily and completely.

  1. Preparation of microporous melamine-based polymer networks in an anhydrous high-temperature miniemulsion.

    PubMed

    Schwab, Matthias Georg; Crespy, Daniel; Feng, Xinliang; Landfester, Katharina; Müllen, Klaus

    2011-11-15

    We report the first example of a successful preparation of a microporous organic polymer within the droplet phase of an inverse non-aqueous miniemulsion. Stable nanoparticles with enhanced specific surface area could be obtained despite the harsh conditions regarding reaction temperature (180 °C) and time (72 h) needed for building melamine-based Schiff base networks. Our new flexible method can in principle be applied to other water-sensitive protocols suitable for the bulk synthesis of MOPs that are based on Friedel-Crafts, Sonogashira-Hagihara or Yamamoto chemistry.

  2. Durable and Hydrophobic Organic-Inorganic Hybrid Coatings via Fluoride Rearrangement of Phenyl T12 Silsesquioxane and Siloxanes.

    PubMed

    Krug, David J; Laine, Richard M

    2017-03-08

    There have been many successful efforts to enhance the water shedding properties of hydrophobic and superhydrophobic coatings, but durability is often a secondary concern. Here, we describe durable and hydrophobic coatings prepared via fluoride catalyzed rearrangement reaction of dodecaphenylsilsesquioxane [PhSiO1.5]12 (DDPS) with octamethylcyclotetrasiloxane (D4). Hydrophobic properties and wear resistance are maximized by incorporating both low surface energy moieties and cross-linkable moieties into the siloxane network. Water contact angles as high as 150 ± 4° were achieved even after 150 wear cycles with SiC sandpaper (2000 grit, 2 kPa). These hybrid organic-inorganic copolymers also have high thermal stabilities after curing at 250 °C (Td5% ≥ 340 °C in air) due to the siloxane network with a maximum Td5% of >460 °C measured for the system with the highest silsesquioxane content. The coating systems presented here offer a unique combination of hydrophobicity and mechanical/thermal stability and could greatly expand the utility of water repellent coatings.

  3. Effective-medium approach for stiff polymer networks with flexible cross-links

    NASA Astrophysics Data System (ADS)

    Broedersz, C. P.; Storm, C.; Mackintosh, F. C.

    2009-06-01

    Recent experiments have demonstrated that the nonlinear elasticity of in vitro networks of the biopolymer actin is dramatically altered in the presence of a flexible cross-linker such as the abundant cytoskeletal protein filamin. The basic principles of such networks remain poorly understood. Here we describe an effective-medium theory of flexibly cross-linked stiff polymer networks. We argue that the response of the cross-links can be fully attributed to entropic stiffening, while softening due to domain unfolding can be ignored. The network is modeled as a collection of randomly oriented rods connected by flexible cross-links to an elastic continuum. This effective medium is treated in a linear elastic limit as well as in a more general framework, in which the medium self-consistently represents the nonlinear network behavior. This model predicts that the nonlinear elastic response sets in at strains proportional to cross-linker length and inversely proportional to filament length. Furthermore, we find that the differential modulus scales linearly with the stress in the stiffening regime. These results are in excellent agreement with bulk rheology data.

  4. Photopolymerization-Induced Phase Separation Process of Thin Composite Films of Liquid Crystal and Polymer Fiber Networks

    NASA Astrophysics Data System (ADS)

    Murashige, Takeshi; Fujikake, Hideo; Ikehata, Seiichiro; Sato, Fumio

    2003-11-01

    It was clarified that a thin composite film of a liquid crystal (LC) and polymer fiber networks can be obtained through two phase separation processes: spinodal decomposition, and nucleation and growth. The phase separation phenomenon was observed using a polarizing microscope under ultraviolet irradiation. Results showed that spinodal decomposition initially occurred in the LC/polymer solution under photopolymerization of a monomer. The polymer fibers were then grown on a surface of solid materials (such as substrates and spacer particles) by the nucleation and growth process in the polymer-rich solution induced by the spinodal decomposition. It was found that the spatially noncyclic morphology of the polymer fibers dispersed in the LC was obtained by the intervention of the nucleation and growth process after the spinodal decomposition process.

  5. Honeycomb structural composite polymer network of gelatin and functional cellulose ester for controlled release of omeprazole.

    PubMed

    Zhuang, Chen; Shi, Chengmei; Tao, Furong; Cui, Yuezhi

    2017-01-05

    The functionalized cellulose ester MCN was firstly synthesized and used to cross-link gelatin by amidation between -NH2 in gelatin and active ester groups in MCN to form a composite polymer network Gel-MCN, which was confirmed by Van Slyke method, FTIR, XRD and TGA-DTG spectra. The model drug omeprazole was loaded in Gel-MCN composites mainly by electrostatic interaction and hydrogen bonds, which were certified by FTIR, XRD and TGA-DSC. Thermal stability, anti-biodegradability, mechanical property and surface hydrophobicity of the composites with different cross-linking extents and drug loading were systematically investigated. SEM images demonstrated the honeycomb structural cells of cross-linked gelatin networks and this ensured drug entrapment. The drug release mechanism was dominated by a combined effect of diffusion and degradation, and the release rate decreased with cross-linking degree increased. The developed drug delivery system had profound significance in improving pesticide effect and bioavailability of drugs.

  6. Tailoring the Structure of Polymer Networks with Photo-Controlled Radical Polymerization

    NASA Astrophysics Data System (ADS)

    Singh, Awaneesh; Kuksenok, Olga; Johnson, Jeremiah A.; Balazs, Anna C.

    Using dissipative particle dynamics (DPD) approach, we developed a novel computational model to study the photo-controlled radical polymerization (photo-CRP) within polymer networks with embedded iniferters. The polymerization process can be turned ``on'' or ``off'' in response to light and the polymerization rate can be modulated by altering the light intensity. This ``photo-growth'' approach allows us to impart changes in the gel network pore size and composition to form photo-tunable smart materials. For example, our approach allows us to design gel composites that are comprised of two distinct layers made of two compatible components at low photo-iniferter concentrations or gel composites that are comprised of two incompatible components that are relatively well intermixed at high photo-iniferter concentration.

  7. Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy

    NASA Technical Reports Server (NTRS)

    Singh, Jag J.; Pater, Ruth H.; Eftekhari, Abe

    1996-01-01

    Thermoset and thermoplastic polyimides have complementary physical and mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. A combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPN) of thermoset LaRC(TM)-RP46 and thermoplastic LaRC(TM)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0:100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical and mechanical properties. As expected, positronium atoms are not formed in these samples. The second lifetime component has been used to infer the positron trap dimensions. The 'free volume' goes through a minimum at a ratio of about 50:50, and this suggests that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples are discussed.

  8. Combined, Independent Small Molecule Release and Shape Memory via Nanogel-Coated Thiourethane Polymer Networks

    PubMed Central

    Dailing, Eric A.; Nair, Devatha P.; Setterberg, Whitney K.; Kyburz, Kyle A.; Yang, Chun; D’Ovidio, Tyler; Anseth, Kristi S.; Stansbury, Jeffrey W.

    2015-01-01

    Drug releasing shape memory polymers (SMPs) were prepared from poly(thiourethane) networks that were coated with drug loaded nanogels through a UV initiated, surface mediated crosslinking reaction. Multifunctional thiol and isocyanate monomers were crosslinked through a step-growth mechanism to produce polymers with a homogeneous network structure that exhibited a sharp glass transition with 97% strain recovery and 96% shape fixity. Incorporating a small stoichiometric excess of thiol groups left pendant functionality for a surface coating reaction. Nanogels with diameter of approximately 10 nm bearing allyl and methacrylate groups were prepared separately via solution free radical polymerization. Coatings with thickness of 10–30 μm were formed via dip-coating and subsequent UV-initiated thiol-ene crosslinking between the SMP surface and the nanogel, and through inter-nanogel methacrylate homopolymerization. No significant change in mechanical properties or shape memory behavior was observed after the coating process, indicating that functional coatings can be integrated into an SMP without altering its original performance. Drug bioactivity was confirmed via in vitro culturing of human mesenchymal stem cells with SMPs coated with dexamethasone-loaded nanogels. This article offers a new strategy to independently tune multiple functions on a single polymeric device, and has broad application toward implantable, minimally invasive medical devices such as vascular stents and ocular shunts, where local drug release can greatly prolong device function. PMID:27066114

  9. Light-induced stress relief to improve flaw tolerance in network polymers

    SciTech Connect

    Long, Kevin N.; Dunn, Martin L.; Scott, Timothy F.; Turpin, Lucas P.; Qi, H. Jerry

    2010-03-15

    We demonstrate the ability to use photoactivated stress relaxation to improve flaw tolerance in network polymers. Unlike most self-healing polymers, which effectively close flaws by locally introducing healing agents (such as uncured resins), here light is used to relax elevated stresses around a flaw before it reaches a critical state, which reduces the threat that the flaw poses to the structural integrity of the material. In this study, we fabricate specimens with well-defined flaws and uniaxially stretch them to failure. By irradiating the specimens with UV light (365 nm) before failure, the nominal strain at failure is increased by 70% and the corresponding nominal stress is increased by 30% compared with nonirradiated specimens. To better understand the phenomena that occur at the multiaxial stress state at the flaw, we model the photomechanics using a recently developed finite element approach that accurately describes the light propagation, photochemistry, radical-induced network evolution, and the mechanical behavior of the material. Model predictions agree well with the experimental results and elucidate the role that photoinduced stress relaxation has on improving flaw tolerance.

  10. Nanocasting Design and Spatially Selective Sulfonation of Polystyrene-Based Polymer Networks as Solid Acid Catalysts.

    PubMed

    Richter, Felix H; Sahraoui, Laila; Schüth, Ferdi

    2016-09-12

    Nanocasting is a general and widely applied method in the generation of porous materials during which a sacrificial solid template is used as a mold on the nanoscale. Ideally, the resulting structure is the inverse of the template. However, replication is not always as direct as anticipated, so the influences of the degree of pore filling and of potential restructuring processes after removal of the template need to be considered. These apparent limitations give rise to opportunities in the synthesis of poly(styrene-co-divinylbenzene) (PSD) polymer networks of widely varying porosities (BET surface area=63-562 m(2)  g(-1) ; Vtot =0.18-1.05 cm(3)  g(-1) ) by applying a single synthesis methodology. In addition, spatially selective sulfonation on the nanoscale seems possible. Together, nanocasting and sulfonation enable rational catalyst design. The highly porous nanocast and predominantly surface-sulfonated PSD networks approach the activity of the corresponding molecular catalyst, para-toluenesulfonic acid, and exceed those of commercial ion-exchange polymers in the depolymerization of macromolecular inulin.

  11. Light-induced stress relief to improve flaw tolerance in network polymers

    NASA Astrophysics Data System (ADS)

    Long, Kevin N.; Dunn, Martin L.; Scott, Timothy F.; Turpin, Lucas P.; Qi, H. Jerry

    2010-03-01

    We demonstrate the ability to use photoactivated stress relaxation to improve flaw tolerance in network polymers. Unlike most self-healing polymers, which effectively close flaws by locally introducing healing agents (such as uncured resins), here light is used to relax elevated stresses around a flaw before it reaches a critical state, which reduces the threat that the flaw poses to the structural integrity of the material. In this study, we fabricate specimens with well-defined flaws and uniaxially stretch them to failure. By irradiating the specimens with UV light (365 nm) before failure, the nominal strain at failure is increased by 70% and the corresponding nominal stress is increased by 30% compared with nonirradiated specimens. To better understand the phenomena that occur at the multiaxial stress state at the flaw, we model the photomechanics using a recently developed finite element approach that accurately describes the light propagation, photochemistry, radical-induced network evolution, and the mechanical behavior of the material. Model predictions agree well with the experimental results and elucidate the role that photoinduced stress relaxation has on improving flaw tolerance.

  12. Molecular template-directed synthesis of microporous polymer networks for highly selective CO2 capture.

    PubMed

    Shi, Yao-Qi; Zhu, Jing; Liu, Xiao-Qin; Geng, Jian-Cheng; Sun, Lin-Bing

    2014-11-26

    Porous polymer networks have great potential in various applications including carbon capture. However, complex monomers and/or expensive catalysts are commonly used for their synthesis, which makes the process complicated, costly, and hard to scale up. Herein, we develop a molecular template strategy to fabricate new porous polymer networks by a simple nucleophilic substitution reaction of two low-cost monomers (i.e., chloromethylbenzene and ethylene diamine). The polymerization reactions can take place under mild conditions in the absence of any catalysts. The resultant materials are interconnected with secondary amines and show well-defined micropores due to the structure-directing role of solvent molecules. These properties make our materials highly efficient for selective CO2 capture, and unusually high CO2/N2 and CO2/CH4 selectivities are obtained. Furthermore, the adsorbents can be completely regenerated under mild conditions. Our materials may provide promising candidates for selective capture of CO2 from mixtures such as flue gas and natural gas.

  13. Carbon nanotubes filled polymer composites: A comprehensive study on improving dispersion, network formation and electrical conductivity

    NASA Astrophysics Data System (ADS)

    Chakravarthi, Divya Kannan

    In this dissertation, we determine how the dispersion, network formation and alignment of carbon nanotubes in polymer nanocomposites affect the electrical properties of two different polymer composite systems: high temperature bismaleimide (BMI) and polyethylene. The knowledge gained from this study will facilitate optimization of the above mentioned parameters, which would further enhance the electrical properties of polymer nanocomposites. BMI carbon fiber composites filled with nickel-coated single walled carbon nanotubes (Ni-SWNTs) were processed using high temperature vacuum assisted resin transfer molding (VARTM) to study the effect of lightning strike mitigation. Coating the SWNTs with nickel resulted in enhanced dispersions confirmed by atomic force microscopy (AFM) and dynamic light scattering (DLS). An improved interface between the carbon fiber and Ni-SWNTs resulted in better surface coverage on the carbon plies. These hybrid composites were tested for Zone 2A lightning strike mitigation. The electrical resistivity of the composite system was reduced by ten orders of magnitude with the addition of 4 weight percent Ni-SWNTs (calculated with respect to the weight of a single carbon ply). The Ni-SWNTs - filled composites showed a reduced amount of damage to simulated lightning strike compared to their unfilled counterparts indicated by the minimal carbon fiber pull out. Methods to reduce the electrical resistivity of 10 weight percent SWNTs --- medium density polyethylene (MDPE) composites were studied. The composites processed by hot coagulation method were subjected to low DC electric fields (10 V) at polymer melt temperatures to study the effect of viscosity, nanotube welding, dispersion and, resultant changes in electrical resistivity. The electrical resistivity of the composites was reduced by two orders of magnitude compared to 10 wt% CNT-MDPE baseline. For effective alignment of SWNTs, a new process called Electric field Vacuum Spray was devised to

  14. Strain Hardening and Strain Softening of Reversibly Cross-linked Supramolecular Polymer Networks.

    PubMed

    Xu, Donghua; Craig, Stephen L

    2011-09-27

    The large amplitude oscillatory shear behavior of metallo-supramolecular polymer networks formed by adding bis-Pd(II) cross-linkers to poly(4-vinylpyridine) (PVP) in dimethyl sulfoxide (DMSO) solution is reported. The influence of scanning frequency, dissociation rate of cross-linkers, concentration of cross-linkers, and concentration of PVP solution on the large amplitude oscillatory shear behavior is explored. In semidilute unentangled PVP solutions, above a critical scanning frequency, strain hardening of both storage moduli and loss moduli is observed. In the semidilute entangled regime of PVP solution, however, strain softening is observed for samples with faster cross-linkers (k(d) ∼ 1450 s(-1)), whereas strain hardening is observed for samples with slower cross-linkers (k(d) ∼ 17 s(-1)). The mechanism of strain hardening is attributed primarily to a strain-induced increase in the number of elastically active chains, with possible contributions from non-Gaussian stretching of polymer chains at strains approaching network fracture. The divergent strain softening of samples with faster cross-linkers in semidilute entangled PVP solutions, relative to the strain hardening of samples with slower cross-linkers, is consistent with observed shear thinning/shear thickening behavior reported previously and is attributed to the fact that the average time that a cross-linker remains detached is too short to permit the local relaxation of polymer chain segments that is necessary for a net conversion of elastically inactive to elastically active cross-linkers. These and other observations paint a picture in which strain softening and shear thinning arise from the same set of molecular mechanisms, conceptually uniting the two nonlinear responses for this system.

  15. Assessing the Strength Enhancement of Heterogeneous Networks of Miscible Polymer Blends

    NASA Astrophysics Data System (ADS)

    Giller, Carl; Roland, Mike

    2013-03-01

    At the typical crosslink densities of elastomers, the failure properties vary inversely with mechanical stiffness, so that compounding entails a compromise between stiffness and strength. Our approach to circumvent this conventional limitation is by forming networks of two polymers that: (i) are thermodynamically miscible, whereby the chemical composition is uniform on the segmental level; and (ii) have markedly different reactivities for network formation. The resulting elastomer consists of one highly crosslinked component and one that is lightly or uncrosslinked. This disparity in crosslinking causes their respective contributions to the network mechanical response to differ diametrically. Earlier results showed some success with this approach for thermally crosslinked blends of 1,2-polybutadiene (PVE) and polyisoprene (PI), as well as ethylene-propylene copolymer (EPM) and ethylene-propylene-diene random terpolymer (EPDM), taking advantage of their differing reactivities to sulfur. In this work we demonstrate the miscibility of polyisobutylene (PIB) with butyl rubber (BR) (a copolymer of PIB and polyisoprene) and show that networks in which only the BR is crosslinked possess greater tensile strengths than neat BR over the same range of moduli. Office of Naval Research

  16. Polymer derived ceramic composites as environmental barrier coatings on steel

    NASA Astrophysics Data System (ADS)

    Torrey, Jessica D.

    Polymer derived ceramics have shown promise as a novel way to process low-dimensional ceramics such as fibers and coatings. They offer advantages over traditional ceramic processing routes including lower pyrolysis temperatures and the ability to employ polymeric processing techniques. The main drawback to preceramic polymers is that they undergo a shrinkage during pyrolysis that can be greater than 50-volume%. One way to overcome this shrinkage is to add filler particles, usually elemental or binary metals, which will expand upon reaction with the pyrolysis atmosphere, thereby compensating for the shrinkage of the polymer. The aim of this study is to develop a polymer derived ceramic composite coating on steel as a barrier to oxidation and carburization, while concurrently gaining insight as to the fundamental mechanisms for compositional and microstructural evolution within the system. A systematic approach to selecting the preceramic polymer and expansion agents was taken. Six commercially available poly(silsesquioxane) polymers and a polysiloxane were studied. Several metals and an intermetallic were considered as potential expansion agents. The most desirable polymer/expansion agent combination was achieved with poly(hydridomethylsiloxane) as the matrix and titanium disilicide as the filler. Processing parameters have been optimized and a relationship derived to predict final coating thickness based on slurry viscosity and dip coating withdrawal speed. Microstructural analysis reveals an amorphous composite coating of oxidized filler particles in a silica matrix. A diffusion layer is visible at the coating-steel interface, indicating good bonding. The optimized coatings are ˜18mum thick, have some residual porosity and a density of 2.57g/cm3. A systematic study of the phase transformations and microstructural changes in the coating and its components during pyrolysis in air is also presented. The system evolves from a polymer filled with a binary metal at

  17. Electron beam exposure mechanisms in hydrogen silsesquioxane investigated by vibrational spectroscopy and in-situ electron beam induced desorption

    SciTech Connect

    Olynick, D.L.; Cord, B.; Schipotinin, A.; Ogletree, D.F.; Schuck, P.J.

    2009-11-13

    Hydrogen Silsesquioxane (HSQ) is used as a high-resolution resist with resolution down below 10nm half-pitch. This material or materials with related functionalities could have widespread impact in nanolithography and nanoscience applications if the exposure mechanism was understood and instabilities controlled. Here we have directly investigated the exposure mechanism using vibrational spectroscopy (both Raman and Fourier transform Infrared) and electron beam desorption spectrocscopy (EBDS). In the non-networked HSQ system, silicon atoms sit at the corners of a cubic structure. Each silicon is bonded to a hydrogen atom and bridges 3 oxygen atoms (formula: HSiO3/2). For the first time, we have shown, via changes in the Si-H2 peak at ~;;2200 cm -1 in the Raman spectra and the release of SiHx products in EBID, that electron-bam exposed materials crosslinks via a redistribution reaction. In addition, we observe the release of significantly more H2 than SiH2 during EBID, which is indicative of additional reaction mechanisms. Additionally, we compare the behavior of HSQ in response to both thermal and electron-beam induced reactions.

  18. Demonstration of a Directly Photopatternable Spin-On-Glass Based on Hydrogen Silsesquioxane and Photobase Generators.

    PubMed

    Harkness; Takeuchi; Tachikawa

    1998-07-28

    A commercially available spin-on-glass material, hydrogen silsesquioxane, has been rendered photopatternable to micrometer dimensions by the introduction of a photobase generator at concentrations of <5 wt %. The cure process proceeds via hydrolysis of the silyl hydride linkage by residual water in the film, as activated by a photogenerated base catalyst. Subsequent reaction of the generated silanol with neighboring silyl hydride groups yields a thermally stable siloxane cross-link. The photochemical cross-linking of hydrogen silsesquioxane shows high sensitivity (<40 mJ/cm2) and is not inhibited by molecular oxygen. The resultant oxide films can be further cured at elevated temperature either under an inert atmosphere to minimize the dielectric constant or heated in an air atmosphere to complete the conversion to silica glass. The oxidative nature of both the photo and thermal cure processes and the release of only traces of hydrogen as byproduct results in minimal weight loss in the film during processing.

  19. Enzymatically degradable hybrid organic-inorganic bridged silsesquioxane nanoparticles for in vitro imaging

    NASA Astrophysics Data System (ADS)

    Fatieiev, Y.; Croissant, J. G.; Julfakyan, K.; Deng, L.; Anjum, D. H.; Gurinov, A.; Khashab, N. M.

    2015-09-01

    We describe biodegradable bridged silsesquioxane (BS) composite nanomaterials with an unusually high organic content (ca. 50%) based on oxamide components mimicking amino acid biocleavable groups. Unlike most bulk BS materials, the design of sub-200 nm nearly monodisperse nanoparticles (NPs) was achieved. These enzymatically degradable BS NPs were further tested as promising imaging nanoprobes.We describe biodegradable bridged silsesquioxane (BS) composite nanomaterials with an unusually high organic content (ca. 50%) based on oxamide components mimicking amino acid biocleavable groups. Unlike most bulk BS materials, the design of sub-200 nm nearly monodisperse nanoparticles (NPs) was achieved. These enzymatically degradable BS NPs were further tested as promising imaging nanoprobes. Electronic supplementary information (ESI) available: Detailed synthetic procedure, experimental procedure and Fig. S1-15. See DOI: 10.1039/c5nr03065j

  20. Photoresponsive Bridged Silsesquioxane Nanoparticles with Tunable Morphology for Light-Triggered Plasmid DNA Delivery.

    PubMed

    Fatieiev, Yevhen; Croissant, Jonas G; Alsaiari, Shahad; Moosa, Basem A; Anjum, Dalaver H; Khashab, Niveen M

    2015-11-18

    Bridged silsesquioxane nanocomposites with tunable morphologies incorporating o-nitrophenylene-ammonium bridges are described. The systematic screening of the sol-gel parameters allowed the material to reach the nanoscale with controlled dense and hollow structures of 100-200 nm. The hybrid composition of silsesquioxanes with 50% organic content homogeneously distributed in the nanomaterials endowed them with photoresponsive properties. Light irradiation was performed to reverse the surface charge of nanoparticles from +46 to -39 mV via a photoreaction of the organic fragments within the particles, as confirmed by spectroscopic monitorings. Furthermore, such nanoparticles were applied for the first time for the on-demand delivery of plasmid DNA in HeLa cancer cells via light actuation.

  1. The structure and bonding properties of chosen phenyl ladder-like silsesquioxane clusters

    NASA Astrophysics Data System (ADS)

    Koleżyński, Andrzej; Jastrzębski, Witold; Szczypka, Wojciech; Kowalewska, Anna; Nowacka, Maria; Sitarz, Maciej

    2013-07-01

    The poly(phenyl silsesquioxanes) were synthesized at 30-36 °C via direct co-hydrolysis and condensation using sequential one batch, two-step reactions in the presence of potassium carbonate as the base catalyst and in the mixture THF/H2O. The structure and properties of the obtained materials were analyzed using NMR, TGA, SEC, XRD and FTIR methods. For chosen ladder-like phenyl silsesquioxane model clusters the DFT calculations by means of Gaussian09 program using B98 (DFT) method and a set 6-31G (d) of basis functions were carried out and respective infrared spectra were constructed and compared with the experimentally obtained ones. The results of topological analysis of total electron density obtained in SCF calculations (Quantum Theory of Atoms in Molecules approach) and structural analysis based on Bond Valence Method were used in detailed analysis of bonding properties in these clusters.

  2. Probing the subglass relaxation behavior in model heterocyclic polymer networks by dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Kramarenko, V. Yu.; Ezquerra, T. A.; Privalko, V. P.

    2001-11-01

    The subglass relaxation (β) in model heterocyclic polymer networks (HPNs) with a controlled ratio of trimerized mono- and diisocyanates was characterized by dielectric spectroscopy in the frequency domain. The β relaxation in the investigated HPNs follows the Arrhenius law with unusually low values of the preexponential factor (10-17<τβ0<10-15 s). However, little influence of the local environment, as characterized by the network density, on the apparent activation energies ΔEβ is observed. This fact, combined with their fairly low absolute values (50.4-58.3 kJ/mol), were considered as typical of a noncooperative relaxation in loosely packed regions of a glassy quasilattice. Both the intensity and dielectric strength of the β relaxation in HPNs increase with increasing apparent network density (i.e., with lower ratios of linear and network structures in the system, L/N). This effect was explained by a model assuming that the total, composition-invariant, free volume available was distributed between densely packed domains comprising linear, two-arm isocyanurate heterocycles (ISHs) and loosely packed, three-arm ISHs, which form continuous, three-dimensional network structures. The experimental data for HPNs confirm Ngai's correlation between the logarithm of the secondary β-relaxation time and the Kohlrausch-Williams-Watts stretching exponent for the primary α relaxation. It is suggested that the absence of conjugated bonds within isocyanurate heterocycles makes them sufficiently flexible to allow for specific conformational transitions, like the ``chair-boat-chair'' transition in the structurally similar cyclohexyl ring.

  3. Effects of Peripheral Architecture on the Properties of Aryl Polyhedral Oligomeric Silsesquioxanes

    DTIC Science & Technology

    2012-07-26

    correlated to POSS assembly, molecular interactions, and the specific attributes of peripheral structure and connectivity to the inorganic core. 15...attributes of peripheral structure and connectivity to the inorganic core. ■ INTRODUCTION Polyhedral oligomeric silsesquioxanes (POSS1) have influenced a...diversity in molecular structures . Such diversity is rooted in the flexibility to manipulate the organic periphery and the size of the POSS core, where

  4. Discontinuous bundling transition in semiflexible polymer networks induced by Casimir interactions

    NASA Astrophysics Data System (ADS)

    Kachan, Devin; Müller, Kei W.; Wall, Wolfgang A.; Levine, Alex J.

    2016-09-01

    Fluctuation-induced interactions are an important organizing principle in a variety of soft matter systems. We investigate the role of fluctuation-based or thermal Casimir interactions between cross linkers in a semiflexible network. One finds that, by integrating out the polymer degrees of freedom, there is an attractive logarithmic potential between nearest-neighbor cross linkers in a bundle, with a significantly weaker next-nearest-neighbor interaction. Here we show that a one-dimensional gas of these strongly interacting linkers in equilibrium with a source of unbound ones admits a discontinuous phase transition between a sparsely and a densely bound bundle. This discontinuous transition induced by the long-ranged nature of the Casimir interaction allows for a similarly abrupt structural transition in semiflexible filament networks between a low cross linker density isotropic phase and a higher cross link density bundle network. We support these calculations with the results of finite element Brownian dynamics simulations of semiflexible filaments and transient cross linkers.

  5. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network.

    PubMed

    Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu

    2014-10-08

    Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers.

  6. Novel biobased photo-crosslinked polymer networks prepared from vegetable oil and 2,5-furan diacrylate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Novel biobased crosslinked polymer networks were prepared from vegetable oil with 2,5-furan diacrylate as a difunctional stiffener through UV photopolymerization, and the mechanical properties of the resulting films were evaluated. The vegetable oil raw materials used were acrylated epoxidized soybe...

  7. Room-Temperature Activation of Hydrogen by Semi-immobilized Frustrated Lewis Pairs in Microporous Polymer Networks.

    PubMed

    Trunk, Matthias; Teichert, Johannes F; Thomas, Arne

    2017-03-15

    Porous polymer networks based on sterically encumbered triphenylphosphine motifs, mimicking the basic sites employed in frustrated Lewis pair (FLP) chemistry, were synthesized via Yamamoto polymerization and their interactions with the strong Lewis acid B(C6F5)3 probed. The combinations yield semi-immobilized FLPs, which are able to cleave dihydrogen heterolytically at ambient temperature and low hydrogen pressure.

  8. Nano-sized Mn oxide/agglomerated silsesquioxane composite as a good catalyst for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Madadkhani, Sepideh

    2016-12-01

    Water splitting to hydrogen and oxygen is an important reaction to store sustainable energies, and water oxidation is identified as the bottleneck for water splitting because it requires the high activation energy to perform. Herein a nano-sized Mn oxide/agglomerated silsesquioxane composite was used to synthesize an efficient catalyst for water oxidation. The composite was synthesized by a straightforward and simple procedure and characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, dynamic light scattering, X-ray diffraction spectrometry, and electrochemical methods. Silsesquioxane causes good dispersion of Mn in the composite. The water-oxidizing activity of this composite was studied in the presence of cerium(IV) ammonium nitrate. The composite at the best calcination temperature (300 °C) shows a turnover frequency 0.3 (mmol O2/mol Mn.s). Regarding the low-cost, environmentally friendly precursors, simple synthesis, and efficiency for water oxidation, the composite is a promising catalyst that can be used in artificial photosynthetic systems for water splitting. We used Agglomerated silsesquioxane as a support for nano-sized Mn oxide to synthesize a good water-oxidizing catalyst.

  9. Dynamic swelling behavior of interpenetrating polymer networks in response to temperature and pH

    PubMed Central

    Slaughter, Brandon V.; Blanchard, Aaron T.; Maass, Katie F.; Peppas, Nicholas A.

    2015-01-01

    Temperature responsive hydrogels based on ionic polymers exhibit swelling transitions in aqueous solutions as a function of shifting pH and ionic strength, in addition to temperature. Applying these hydrogels to useful applications, particularly for biomedical purposes such as drug delivery and regenerative medicine, is critically dependent on understanding the hydrogel solution responses as a function of all three parameters together. In this work, interpenetrating polymer network (IPN) hydrogels of polyacrylamide and poly(acrylic acid) were formulated over a broad range of synthesis variables using a fractional factorial design, and were examined for equilibrium temperature responsive swelling in a variety of solution conditions. Due to the acidic nature of these IPN hydrogels, usable upper critical solution temperature (UCST) responses for this system occur in mildly acidic environments. Responses were characterized in terms of maximum equilibrium swelling and temperature-triggered swelling using turbidity and gravimetric measurements. Additionally, synthesis parameters critical to achieving optimal overall swelling, temperature-triggered swelling, and sigmoidal temperature transitions for this IPN system were analyzed based on the fractional factorial design used to formulate these hydrogels. PMID:26405349

  10. The synthesis of hydrogels with controlled distribution of polymer brushes in hydrogel network

    NASA Astrophysics Data System (ADS)

    Sun, YuWei; Zhou, Chao; Zhang, AoKai; Xu, LiQun; Yao, Fang; Cen, Lian; Fu, Guo-Dong

    2014-11-01

    Poly(ethylene glycol) (PEG) hydrogels with 3-dimensionally controlled well-defined poly(N-isopropylacrylamide) (poly(NIPAAm)) brushes were prepared by combined copper(I)-catalyzed azide-alkyne cycloaddition ("Click Chemistry") and atom transfer radical polymerization (ATRP). The resulting hydrogels were presented as representatives with their detailed synthesis routes and characterization. HPEG-S-poly(NIPAAm) is a hydrogel with poly(NIPAAm) brushes mainly grafted on surface, whereas HPEG-G-poly(NIPAAm) has a gradiently decreased poly(NIPAAm) brushes in their chain length from surface to inside. On the other hand, poly(NIPAAm) brushes in HPEG-U-poly(NIPAAm) are uniformly dispersed throughout the whole hydrogel network. Successful preparation of HPEG-S-poly(NIPAAm), HPEG-G-poly(NIPAAm) and HPEG-U-poly(NIPAAm) were ascertained by X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. Optical properties and thermal behaviors of these hydrogels were evaluated by UV-visible transmittance spectra and differential scanning calorimetry (DSC). Hence, the flexibility and controllability of the synthetic strategy in varying the distribution of polymer brushes and hydrogel properties was demonstrated. Hydrogels with tunable and well-defined 3-dimensional poly(NIPAAm) polymer brushes could be tailor-designed to find potential applications in smart devices or skin dressing, such as for diabetics as they have special optical and thermal behaviors.

  11. In silico design of porous polymer networks: high-throughput screening for methane storage materials.

    PubMed

    Martin, Richard L; Simon, Cory M; Smit, Berend; Haranczyk, Maciej

    2014-04-02

    Porous polymer networks (PPNs) are a class of advanced porous materials that combine the advantages of cheap and stable polymers with the high surface areas and tunable chemistry of metal-organic frameworks. They are of particular interest for gas separation or storage applications, for instance, as methane adsorbents for a vehicular natural gas tank or other portable applications. PPNs are self-assembled from distinct building units; here, we utilize commercially available chemical fragments and two experimentally known synthetic routes to design in silico a large database of synthetically realistic PPN materials. All structures from our database of 18,000 materials have been relaxed with semiempirical electronic structure methods and characterized with Grand-canonical Monte Carlo simulations for methane uptake and deliverable (working) capacity. A number of novel structure-property relationships that govern methane storage performance were identified. The relationships are translated into experimental guidelines to realize the ideal PPN structure. We found that cooperative methane-methane attractions were present in all of the best-performing materials, highlighting the importance of guest interaction in the design of optimal materials for methane storage.

  12. Revealing the Supramolecular Nature of Side-Chain Terpyridine-Functionalized Polymer Networks

    PubMed Central

    Brassinne, Jérémy; Jochum, Florian D.; Fustin, Charles-André; Gohy, Jean-François

    2015-01-01

    Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylamino)ethyl methacrylate) is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks. PMID:25569082

  13. Effects of polymer networks on physical properties of epoxy molding compounds

    SciTech Connect

    Eguchi, S.; Nagai, A.; Ishii, T.

    1996-10-01

    IC and LSI plastic packages are being changed from pin insertion to surface mounting types with increasing bit density. In their surface mounting technology, the most significant subject is preventing package cracks which occur when soldering temperatures are from 215 to 260{degrees}C. Effects of Polymer networks on physical properties of epoxy molding compounds are examined to improve the resistance to package cracks in the soldering process. Lowering the moisture absorption of compounds and increasing their adhesion are identified as effective methods. Since resins with a low moisture absorption and a high adhesion tend to have a low crosslinking density, the resin with a relatively low crosslinking density is chosen as a candidate for the encapsulating compound. The new epoxy molding compounds, while providing a high cohesive energy and a bulky structure inside the resin, can have a higher glass transition temperature in the relatively low crosslinking density.

  14. Multifunctional membranes for solvent resistant nanofiltration and pervaporation applications based on segmented polymer networks.

    PubMed

    Li, Xianfeng; Basko, Malgorzata; Du Prez, S Filip; Vankelecom, Ivo F J

    2008-12-25

    Hydrophilic bis(acrylate)-terminated poly(ethylene oxide) was used as macromolecular cross-linker of different hydrophobic polyacrylates for the synthesis of amphiphilic segmented polymer networks (SPNs). Multifunctional composite membranes with thin SPN toplayers were prepared by in situ polymerization. As the support consisted of hydrolyzed polyacrylonitrile, the high chemical resistance of the composite membrane allowed applications of the SPN-based membranes in solvent-resistant nanofiltration (SRNF) and pervaporation (PV). The membranes show very high retention on Rose Bengal (RB) in different solvents, especially in strong swelling solvents such as tetrahydrofuran (THF) and dimethylformamide (DMF). The membranes were also tested in pervaporation for dehydration of ethanol and isopropanol (IPA). The selectivity of the membranes greatly depends on the composition or the ratio of the hydrophilic and hydrophobic phases of the SPN.

  15. Segmenting delaminations in carbon fiber reinforced polymer composite CT using convolutional neural networks

    NASA Astrophysics Data System (ADS)

    Sammons, Daniel; Winfree, William P.; Burke, Eric; Ji, Shuiwang

    2016-02-01

    Nondestructive evaluation (NDE) utilizes a variety of techniques to inspect various materials for defects without causing changes to the material. X-ray computed tomography (CT) produces large volumes of three dimensional image data. Using the task of identifying delaminations in carbon fiber reinforced polymer (CFRP) composite CT, this work shows that it is possible to automate the analysis of these large volumes of CT data using a machine learning model known as a convolutional neural network (CNN). Further, tests on simulated data sets show that with a robust set of experimental data, it may be possible to go beyond just identification and instead accurately characterize the size and shape of the delaminations with CNNs.

  16. Rheological and chemical analysis of reverse gelation in a covalently crosslinked Diels-Alder polymer network

    PubMed Central

    Adzima, Brian J.; Aguirre, H. Alan; Kloxin, Christopher J.; Scott, Timothy F.; Bowman, Christopher N.

    2009-01-01

    A network polymer, incorporating dynamic and reversible crosslinks, was synthesized using the Diels-Alder reaction. Fourier transform infrared (FTIR) spectroscopy was used to characterize the reaction rate and thermodynamic equilibrium over a broad temperature range. Equilibrium conversion of the furan and maleimide varied from 74% at 85°C to 24% at 155°C, demonstrating significant depolymerization via the retro-Diels-Alder reaction. The gel point temperature, as determined by rheometry using the Winter-Chambon criterion, was 92°C, corresponding to a gel-point conversion of 71%, consistent with the Flory-Stockmayer equation. The scaling exponents for the complex moduli, viscosity, and plateau modulus, in the vicinity of the gel-point, were determined and compared with experimental and theoretical literature values. Further, the material exhibited a low frequency relaxation owing to dynamic rearrangement of crosslinks by the Diels-Alder and retro-Diels-Alder reactions. PMID:20711364

  17. New theoretical considerations in polymer rheology: Elastic breakdown of chain entanglement network

    NASA Astrophysics Data System (ADS)

    Wang, Shi-Qing; Ravindranath, Sham; Wang, Yangyang; Boukany, Pouyan

    2007-08-01

    Recent experimental evidence has motivated us to present a set of new theoretical considerations and to provide a rationale for interpreting the intriguing flow phenomena observed in entangled polymer solutions and melts [P. Tapadia and S. Q. Wang, Phys. Rev. Lett. 96, 016001 (2006); 96, 196001 (2006); S. Q. Wang et al., ibid. 97, 187801 (2006)]. Three forces have been recognized to play important roles in controlling the response of a strained entanglement network. During flow, an intermolecular locking force fiml arises and causes conformational deformation in each load-bearing strand between entanglements. The chain deformation builds up a retractive force fretract within each strand. Chain entanglement prevails in quiescence because a given chain prefers to stay interpenetrating into other chains within its pervaded volume so as to enjoy maximum conformational entropy. Since each strand of length lent has entropy equal to kBT, the disentanglement criterion is given by fretract>fent~kBT/lent in the case of interrupted deformation. This condition identifies fent as a cohesive force. Imbalance among these forces causes elastic breakdown of the entanglement network. For example, an entangled polymer yields during continuous deformation when the declining fiml cannot sustain the elevated fretract. This opposite trend of the two forces is at the core of the physics governing a ``cohesive'' breakdown at the yield point (i.e., the stress overshoot) in startup flow. Identifying the yield point as the point of force imbalance, we can also rationalize the recently observed striking scaling behavior associated with the yield point in continuous deformation of both shear and extension.

  18. Linear viscoelastic properties of transient networks formed by associating polymers with multiple stickers

    NASA Astrophysics Data System (ADS)

    Indei, Tsutomu; Takimoto, Jun-ichi

    2010-11-01

    We have developed a single-chain theory that describes dynamics of associating polymer chains carrying multiple associative groups (or stickers) in the transient network formed by themselves and studied linear viscoelastic properties of this network. It is shown that if the average number N¯ of stickers associated with the network junction per chain is large, the terminal relaxation time τA that is proportional to τXN¯2 appears. The time τX is the interval during which an associated sticker goes back to its equilibrium position by one or more dissociation steps. In this lower frequency regime ω <1/τX, the moduli are well described in terms of the Rouse model with the longest relaxation time τA. The large value of N¯ is realized for chains carrying many stickers whose rate of association with the network junction is much larger than the dissociation rate. This associative Rouse behavior stems from the association/dissociation processes of stickers and is different from the ordinary Rouse behavior in the higher frequency regime, which is originated from the thermal segmental motion between stickers. If N¯ is not large, the dynamic shear moduli are well described in terms of the Maxwell model characterized by a single relaxation time τX in the moderate and lower frequency regimes. Thus, the transition occurs in the viscoelastic relaxation behavior from the Maxwell-type to the Rouse-type in ω <1/τX as N¯ increases. All these results are obtained under the affine deformation assumption for junction points. We also studied the effect of the junction fluctuations from the affine motion on the plateau modulus by introducing the virtual spring for bound stickers. It is shown that the plateau modulus is not affected by the junction fluctuations.

  19. Study of diffusion in polymer solutions and networks by fluorescence correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Chehreghanianzabi, Yasaman

    Diffusion in polymer solutions and networks is a topic of vast importance in many fields related to medical devices, tissue engineering, and drug delivery. Understanding diffusion in such environments is also essential for describing molecular transport through biological systems such as cells and tissues. Fluorescence correlation spectroscopy (FCS) is single molecule spectroscopic technique that measures the fluctuations of fluorescent probes in a defined confocal volume and correlates them in time to give information on diffusion times, concentrations, and interactions as well as indirectly, on macromolecular structure or conformation. In the first project we used diffusivity data obtained by FCS to develop a novel homogenization theory model to accurately predict solute diffusivity in polymer solutions. We focused on a setting where diffusivity was hindered by obstruction only. By choosing experimental conditions that satisfied the model assumptions, we were able to validate the homogenization theory model. While testing diffusivity in various polymer solutions, we also observed an unexpected phenomenon--a dramatic decrease in diffusivity of small fluorophores in dilute solutions of polyethylene glycol (PEG), which led to the second project. Here, we determined that the rapid drop was due to a complexation between the PEG and the fluorophore. We also determined that this complexation was highly specific and could be attributed to hydrogel bonding between the ether oxygen of PEG and the carboxylic hydrogen of the fluorophore. We then transitioned to a more complex hydrogel network environment, namely fluorophore diffusivity in various alginate hydrogels--varied by concentration and modifications with a cell adhesive ligand. Importantly, we were able to determine that while the fluorophore diffusivity was hindered due to electrostatic interactions, it was the same irrespective of the alginate concentration or modifications. The last part of this thesis was focused

  20. Contribution toward comprehension of contact angle values on single polydimethylsiloxane and poly(ethylene oxide) polymer networks.

    PubMed

    Bouteau, Murielle; Cantin, Sophie; Fichet, Odile; Perrot, Françoise; Teyssié, Dominique

    2010-11-16

    The large application ranges of polydimethylsiloxane (PDMS) and poly(ethylene oxide) (PEO) based materials justify the importance of controlling polymer surface properties including morphology and wettability behavior. However, it appears that the reported contact angle values of PDMS surfaces show significant scattering which cannot always be interpreted in terms of sole chemical data. In addition, few values are reported concerning pure PEO surfaces, since the polymer generally swells in the presence of water. Thus, in order to correlate surface properties with sample preparation, several single PDMS and PEO polymer networks were synthesized with varying cross-linkers and different cross-linking densities. First, the sample surface topography was systematically analyzed by atomic force microscopy (AFM). It was proven that the removal process of the polymer film from the mold plays a significant role in surface topography according to the vitreous or rubbery state of the given polymer network at room temperature irrespective of mold surface treatment. AFM-scale smooth surfaces can be obtained for all the samples by removing them systematically from the mold at a temperature below the α-relaxation temperature. Dynamic water contact angles were then measured and the values analyzed as a function of cross-linker nature and cross-linking density.

  1. Shape-Memory Hydrogels: Evolution of Structural Principles To Enable Shape Switching of Hydrophilic Polymer Networks.

    PubMed

    Löwenberg, Candy; Balk, Maria; Wischke, Christian; Behl, Marc; Lendlein, Andreas

    2017-02-15

    The ability of hydrophilic chain segments in polymer networks to strongly interact with water allows the volumetric expansion of the material and formation of a hydrogel. When polymer chain segments undergo reversible hydration depending on environmental conditions, smart hydrogels can be realized, which are able to shrink/swell and thus alter their volume on demand. In contrast, implementing the capacity of hydrogels to switch their shape rather than volume demands more sophisticated chemical approaches and structural concepts. In this Account, the principles of hydrogel network design, incorporation of molecular switches, and hydrogel microstructures are summarized that enable a spatially directed actuation of hydrogels by a shape-memory effect (SME) without major volume alteration. The SME involves an elastic deformation (programming) of samples, which are temporarily fixed by reversible covalent or physical cross-links resulting in a temporary shape. The material can reverse to the original shape when these molecular switches are affected by application of a suitable stimulus. Hydrophobic shape-memory polymers (SMPs), which are established with complex functions including multiple or reversible shape-switching, may provide inspiration for the molecular architecture of shape-memory hydrogels (SMHs), but cannot be identically copied in the world of hydrophilic soft materials. For instance, fixation of the temporary shape requires cross-links to be formed also in an aqueous environment, which may not be realized, for example, by crystalline domains from the hydrophilic main chains as these may dissolve in presence of water. Accordingly, dual-shape hydrogels have evolved, where, for example, hydrophobic crystallizable side chains have been linked into hydrophilic polymer networks to act as temperature-sensitive temporary cross-links. By incorporating a second type of such side chains, triple-shape hydrogels can be realized. Considering the typically given light

  2. Tailoring the Kinetics of the Photoinitiated Cationic Polymerization of Polyoctahedral Oligomeric Silsesquioxane (POSS)-Containing Epoxy Monomers

    NASA Astrophysics Data System (ADS)

    Iordanov, Liubomir

    The effect of low-viscosity reactive diluents on the UV-curing kinetics of the photoinitiated cationic polymerization of a polyhedral oligomeric silsesquioxane molecule having 8 glycidyl substituents (glycidyl POSS) was examined. This compound has many beneficial properties such hardness, scratch resistance, and high thermal stability, which make it suitable for UV coating applications. However, these properties are outweighed by a high viscosity that causes diffusion limitations, thus lowering the rate of polymerization. 3,3'-(oxybis(methylene))bis(3-ethyloxetane) (DOX), Limonene Dioxide (LDO), and alpha-Pinene Oxide (alphaPO) were all used as reactive diluents. Glycidyl POSS was copolymerized with each and the effect of weight percent (wt% ) composition and viscosity on the overall polymer reactivity was evaluated. The progress of the reaction was measured using optical pyrometry, and viscosity was measured using a cone-and-plate viscometer. Shear rheological studies were used to monitor the thermal curing behavior of glycidyl POSS with and without photoinitiator. The induction time (tind) and time at peak reaction temperature (tpeak) were both used to observe the progress of the reaction. At any given composition of diluent, DOX performed better than either LDO or alphaPO; DOX needed only 20 wt% dilution to show a definite induction time, whereas LDO needed almost 50 wt% dilution to produce the same effect. Similarly, LDO showed reaction times that were at least twice as long as those of DOX when compared at the same viscosity. These results successfully demonstrate that through simple copolymerization with reactive diluents, the viscosity and reactivity of glycidyl POSS can be tailored to enhance its practical use in UV coating applications.

  3. An annulus fibrosus closure device based on a biodegradable shape-memory polymer network.

    PubMed

    Sharifi, Shahriar; van Kooten, Theo G; Kranenburg, Hendrik-Jan C; Meij, Björn P; Behl, Marc; Lendlein, Andreas; Grijpma, Dirk W

    2013-11-01

    Injuries to the intervertebral disc caused by degeneration or trauma often lead to tearing of the annulus fibrosus (AF) and extrusion of the nucleus pulposus (NP). This can compress nerves and cause lower back pain. In this study, the characteristics of poly(D,L-lactide-co-trimethylene carbonate) networks with shape-memory properties have been evaluated in order to prepare biodegradable AF closure devices that can be implanted minimally invasively. Four different macromers with (D,L-lactide) to trimethylene carbonate (DLLA:TMC) molar ratios of 80:20, 70:30, 60:40 and 40:60 with terminal methacrylate groups and molecular weights of approximately 30 kg mol(-1) were used to prepare the networks by photo-crosslinking. The mechanical properties of the samples and their shape-memory properties were determined at temperatures of 0 °C and 40 °C by tensile tests- and cyclic, thermo-mechanical measurements. At 40 °C all networks showed rubber-like behavior and were flexible with elastic modulus values of 1.7-2.5 MPa, which is in the range of the modulus values of human annulus fibrosus tissue. The shape-memory characteristics of the networks were excellent with values of the shape-fixity and the shape-recovery ratio higher than 98 and 95%, respectively. The switching temperatures were between 10 and 39 °C. In vitro culture and qualitative immunocytochemistry of human annulus fibrosus cells on shape-memory films with DLLA:TMC molar ratios of 60:40 showed very good ability of the networks to support the adhesion and growth of human AF cells. When the polymer network films were coated by adsorption of fibronectin, cell attachment, cell spreading, and extracellular matrix production was further improved. Annulus fibrosus closure devices were prepared from these AF cell-compatible materials by photo-polymerizing the reactive precursors in a mold. Insertion of the multifunctional implant in the disc of a cadaveric canine spine showed that these shape-memory devices could be

  4. Preparation and characterization of shape memory composite foams with interpenetrating polymer networks

    NASA Astrophysics Data System (ADS)

    Yao, Yongtao; Zhou, Tianyang; Yang, Cheng; Liu, Yanju; Leng, Jinsong

    2016-03-01

    The present study reports a feasible approach of fabricating shape memory composite foams with an interpenetrating polymer network (IPN) based on polyurethane (PU) and shape memory epoxy resin (SMER) via a simultaneous polymerization technique. The PU component is capable of constructing a foam structure and the SMER is grafted on the PU network to offer its shape memory property in the final IPN foams. A series of IPN foams without phase separation were produced due to good compatibility and a tight chemical interaction between PU and SMER components. The relationships of the geometry of the foam cell were investigated via varying compositions of PU and SMER. The physical property and shape memory property were also evaluated. The stimulus temperature of IPN shape memory composite foams, glass temperature (Tg), could be tunable by varying the constituents and Tg of PU and SMER. The mechanism of the shape memory effect of IPN foams has been proposed. The shape memory composite foam with IPN developed in this study has the potential to extend its application field.

  5. Controlling Phase Separation of Interpenetrating Polymer Networks by Addition of Block Copolymers

    NASA Astrophysics Data System (ADS)

    Rohde, Brian; Krishnamoorti, Ramanan; Robertson, Megan

    2015-03-01

    Interpenetrating polymer networks (IPNs) offer a unique way to produce mechanically superior thermoset blends relative to the neat components. In this study, IPNs were prepared consisting of polydicyclopentadiene (polyDCPD), contributing high fracture toughness, and an epoxy resin (the diglycidyl ether of bisphenol A cured with nadic methyl anhydride), contributing high tensile strength and modulus. In the absence of compatibilization, the simultaneous curing of the networks leads to a macroscopically phase separated blend that exhibits poor mechanical behavior. To control phase separation and drive the system towards more mechanically robust nanostructured IPNs, block copolymers were designed to compatibilize this system, where one block possesses affinity to polyDCPD (polynorbornene in this study) and the other block possesses affinity to DGEBA (poly(ɛ-caprolactone) in this study). The influence of the block copolymer composition on the degree of phase separation and interfacial adhesion in the IPN was studied using a combination of small-angle scattering and imaging techniques. The resultant mechanical properties were explored and structure-property relationships were developed in this blend system.

  6. Characterization and preparation of p(U-MMA-An) interpenetrating polymer network damping and absorbing material.

    PubMed

    Liu, Jun; Li, Qingshan; Zhuo, Yuguo; Hong, Wei; Lv, Wenfeng; Xing, Guangzhong

    2014-06-01

    P(U-MMA-ANI) interpenetrating polymer network (IPN) damping and absorbing material is successfully synthesized by PANI particles served as an absorbing agent with the microemulsion polymerization and P(U-MMA) foam IPN network structure for substrate materials with foaming way. P(U-MMA-ANI) IPN is characterized by the compression mechanical performance testing, TG-DSC, and DSC. The results verify that the P(U-MMA) IPN foam damping material has a good compressive strength and compaction cycle property, and the optimum content of PMMA was 40% (mass) with which the SEM graphs do not present the phase separation on the macro level between PMMA and PU, while the phase separation was observed on the micro level. The DTG curve indicates that because of the formation of P(U-MMA) IPN, the decomposition temperature of PMMA and the carbamate in PU increases, while that of the polyol segment in PU has almost no change. P(U-MMA-ANI) IPN foam damping and absorbing material is obtained by PANI particles served as absorbing agent in the form of filler, and PMMA in the form of micro area in substrate material. When the content of PANI was up to 2.0% (mass), the dissipation factor of composites increased, and with the increasing of frequency the dissipation factor increased in a straight line.

  7. On the Mass Fractal Character of Si-Based Structural Networks in Amorphous Polymer Derived Ceramics

    PubMed Central

    Sen, Sabyasachi; Widgeon, Scarlett

    2015-01-01

    The intermediate-range packing of SiNxC4−x (0 ≤ x ≤ 4) tetrahedra in polysilycarbodiimide and polysilazane-derived amorphous SiCN ceramics is investigated using 29Si spin-lattice relaxation nuclear magnetic resonance (SLR NMR) spectroscopy. The SiCN network in the polysilylcarbodiimide-derived ceramic consists predominantly of SiN4 tetrahedra that are characterized by a 3-dimensional spatial distribution signifying compact packing of such units to form amorphous Si3N4 clusters. On the other hand, the SiCN network of the polysilazane-derived ceramic is characterized by mixed bonded SiNxC4−x tetrahedra that are inefficiently packed with a mass fractal dimension of Df ~2.5 that is significantly lower than the embedding Euclidean dimension (D = 3). This result unequivocally confirms the hypothesis that the presence of dissimilar atoms, namely, 4-coordinated C and 3-coordinated N, in the nearest neighbor environment of Si along with some exclusion in connectivity between SiCxN4−x tetrahedra with widely different N:C ratios and the absence of bonding between C and N result in steric hindrance to an efficient packing of these structural units. It is noted that similar inefficiencies in packing are observed in polymer-derived amorphous SiOC ceramics as well as in proteins and binary hard sphere systems.

  8. Ice-Templated Assembly Strategy to Construct 3D Boron Nitride Nanosheet Networks in Polymer Composites for Thermal Conductivity Improvement.

    PubMed

    Zeng, Xiaoliang; Yao, Yimin; Gong, Zhengyu; Wang, Fangfang; Sun, Rong; Xu, Jianbin; Wong, Ching-Ping

    2015-12-01

    Owing to the growing heat removal issue of modern electronic devices, polymer composites with high thermal conductivity have drawn much attention in the past few years. However, a traditional method to enhance the thermal conductivity of the polymers by addition of inorganic fillers usually creates composite with not only limited thermal conductivity but also other detrimental effects due to large amount of fillers required. Here, novel polymer composites are reported by first constructing 3D boron nitride nanosheets (3D-BNNS) network using ice-templated approach and then infiltrating them with epoxy matrix. The obtained polymer composites exhibit a high thermal conductivity (2.85 W m(-1) K(-1)), a low thermal expansion coefficient (24-32 ppm K(-1)), and an increased glass transition temperature (T(g)) at relatively low BNNSs loading (9.29 vol%). These results demonstrate that this approach opens a new avenue for design and preparation of polymer composites with high thermal conductivity. The polymer composites are potentially useful in advanced electronic packaging techniques, namely, thermal interface materials, underfill materials, molding compounds, and organic substrates.

  9. A study of random resistor-capacitor-diode networks to assess the electromagnetic properties of carbon nanotube filled polymers

    NASA Astrophysics Data System (ADS)

    Bychanok, D. S.; Paddubskaya, A. G.; Kuzhir, P. P.; Maksimenko, S. A.; Brosseau, C.; Macutkevic, J.; Bellucci, S.

    2013-12-01

    We determined the frequency dependent effective permittivity of a large ternary network of randomly positioned resistors, capacitors, and diodes. A linear circuit analysis of such systems is shown to match the experimental dielectric response of single-walled carbon nanotube (SWCNT) filled polymers. This modeling method is able to reproduce the two most important features of SWCNT filled composites, i.e., the low frequency dispersion and dipolar relaxation. As a result of the modeling important physical conclusion proved by the experimental data was done: the low frequency behavior of SWCNT-filled polymer composites is mostly caused by the fraction of semiconducting SWCNTs.

  10. Mechanical behavior of highly cross-linked polymer networks and its links to microscopic structure.

    PubMed

    Mukherji, Debashish; Abrams, Cameron F

    2009-06-01

    Highly cross-linked polymer (HCP) networks are becoming increasingly important as high-performance adhesives and multifunctional composite materials. Because of their cross-linked molecular architectures, HCPs can be strong but brittle. One key goal in improving the performance of an HCP is to increase toughness without sacrificing strength. Using large scale molecular-dynamics simulation, we compare and characterize the mechanical behavior of two model HCPs under tensile deformation. In the first case, bond angles among any three connected monomers are unconstrained and in the second case we impose harmonic tetrahedral bond angle constraints. We perform a detailed microstructural analysis that establishes a unique correlation between macroscopic mechanical behavior and the microscopic structure of an HCP. While, in the unconstrained system, strain-hardening behavior is observed that is attributed to the formation of microvoids, the void growth is completely arrested in the constrained system and no strain hardening is observed. Moreover, after the initial strain-hardening phase, the unconstrained system displays the same stress-strain behavior as that of a constrained network. Strain hardening makes the unconstrained system ductile while it retains the same tensile strength as the constrained system. We suggest that bond angle flexibility of cross-linkers might be a possible means to control ductility in an HCP network at a constant cross-linker density. We have also studied the effect of temperature, strain rate, and intermonomer nonbonded interaction strength on the stress-strain behavior. Interestingly at a strong intermonomer nonbonded interaction strength, no strain hardening is observed even in the unconstrained system and fracture sets in at around 1% strain, similar to what is observed in an experimental system such as epoxy and vinyl-ester based thermosets. This indicates that strong nonbonded interactions play a key role in making an HCP strong but

  11. Polymerization of Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers

    DTIC Science & Technology

    2012-12-01

    mm Methanol Octane Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007, 318, 1618 Superamphiphobic...allow for functionalization of F-POSS – Open door for use a building block material for low surface energy materials • Applications – Mechanical...robust superhydrophobic /oleophobic/omniphobic surfaces • Via covalently attached F-POSS to substrate (surface, nanoparticle, polymer matrix) – Effects

  12. Enhanced performance of polymer solar cell with ZnO nanoparticle electron transporting layer passivated by in situ cross-linked three-dimensional polymer network

    NASA Astrophysics Data System (ADS)

    Wu, Zhongwei; Song, Tao; Xia, Zhouhui; Wei, Huaixin; Sun, Baoquan

    2013-12-01

    An in situ cross-linked three-dimensional polymer network has been developed to passivate ZnO nanoparticles as an electron transporting layer (ETL) to improve the performance of inverted organic solar cells. The passivated ZnO ETL-based devices achieve efficiencies of 3.26% for poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and 7.37% for poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl

  13. Comparative characterization of a novel cad-cam polymer-infiltrated-ceramic-network

    PubMed Central

    Pascual, Agustín; Camps, Isabel; Grau-Benitez, María

    2015-01-01

    Background The field of dental ceramics for CAD-CAM is enriched with a new innovative material composition having a porous three-dimensional structure of feldspathic ceramic infiltrated with acrylic resins.The aim of this study is to determine the mechanical properties of Polymer-Infiltrated-Ceramic-Network (PICN) and compare its performance with other ceramics and a nano-ceramic resin available for CAD-CAM systems. Material and Methods In this study a total of five different materials for CAD-CAM were investigated. A polymer-infiltrated ceramic (Vita Enamic), a nano-ceramic resin (Lava Ultimate), a feldspathic ceramic (Mark II), a lithium disilicate ceramic (IPS-e max CAD) and finally a Leucite based ceramic (Empress - CAD). From CAD-CAM blocks, 120 bars (30 for each material cited above) were cut to measure the flexural strength with a three-point-bending test. Strain at failure, fracture stress and Weibull modulus was calculated. Vickers hardness of each material was also measured. Results IPS-EMAX presents mechanical properties significantly better from the other materials studied. Its strain at failure, flexural strength and hardness exhibited significantly higher values in comparison with the others. VITA ENAMIC and LAVA ULTIMATE stand out as the next most resistant materials. Conclusions The flexural strength, elastic modulus similar to a tooth as well as having less hardness than ceramics make PICN materials an option to consider as a restorative material. Key words:Ceramic infiltrated with resin, CAD-CAM, Weibull modulus, flexural strength, micro hardness. PMID:26535096

  14. Photothermal triggering of self-healing processes applied to the reparation of bio-based polymer networks

    NASA Astrophysics Data System (ADS)

    Altuna, F. I.; Antonacci, J.; Arenas, G. F.; Pettarin, V.; Hoppe, C. E.; Williams, R. J. J.

    2016-04-01

    Green laser irradiation successfully activated self-healing processes in epoxy-acid networks modified with low amounts of gold nanoparticles (NPs). A bio-based polymer matrix, obtained by crosslinking epoxidized soybean oil (ESO) with an aqueous citric acid (CA) solution, was self-healed through molecular rearrangements produced by transesterification reactions of β-hydroxyester groups generated in the polymerization reaction. The temperature increase required for the triggering of these thermally activated reactions was attained by green light irradiation of the damaged area. Compression force needed to assure a good contact between crack faces was achieved by volume dilatation generated by the same temperature rise. Gold NPs dispersed in the polymer efficiently generated heat in the presence of electromagnetic radiation under plasmon resonance, acting as nanometric heating sources and allowing remote activation of the self-healing in the crosslinked polymer.

  15. A multicolor photoinitiator for cationic polymerization and interpenetrated polymer network synthesis: 2,7-di-tert-butyldimethyldihydropyrene.

    PubMed

    Tehfe, Mohamad-Ali; Dumur, Frédéric; Vilà, Neus; Graff, Bernadette; Mayer, Cédric R; Fouassier, Jean Pierre; Gigmes, Didier; Lalevée, Jacques

    2013-07-12

    For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As a consequence, several photoinitiators are necessary to harvest all of the emitted visible photons. Herein, 2,7-di-tert-butyldimethyldihydropyrene is used for the first time as a multicolor photoinitiator for the cationic polymerization of epoxides. Upon addition of diphenyliodonium hexafluorophosphate and optionally N-vinylcarbazole, the originality of this approach is to allow efficient monomer conversions under various excitation light sources in the 360-650 nm wavelength range: halogen lamps, and light-emitting and laser diodes. The synthesis of an interpenetrated polymer network from an epoxide/acrylate blend using a red light at 635 nm is also feasible. The formed polymer material exhibits a photochromic character.

  16. A New Star-shaped Carbazole Derivative with Polyhedral Oligomeric Silsesquioxane Core: Crystal Structure and Unique Photoluminescence Property.

    PubMed

    Xu, Zixuan; Yu, Tianzhi; Zhao, Yuling; Zhang, Hui; Zhao, Guoyun; Li, Jianfeng; Chai, Lanqin

    2016-01-01

    A new inorganic–organic hybrid material based on polyhedral oligomeric silsesquioxane (POSS) capped with carbazolyl substituents, octakis[3-(carbazol-9-yl)propyldimethylsiloxy]-silsesquioxane (POSS-8Cz), was successfully synthesized and characterized. The X-ray crystal structure of POSS-8Cz were described. The photophysical properties of POSS-8Cz were investigated by using UV–vis,photoluminescence spectroscopic analysis. The hybrid material exhibits blue emission in the solution and the solid film.The morphology and thermal stablity properties were measured by X-ray diffraction (XRD) and TG-DTA analysis.

  17. Optimizing Glassy Polymer Network Morphology for Nano-particle Dispersion, Stabilization and Performance

    DTIC Science & Technology

    2016-10-03

    dispersity and polymerization pathway, Moskowitz, Jeremy and Wiggins, Jeffrey, Polymer Degradation and Stability 2016, 125, 76 iv. High Molecular... polymerization pathway, Moskowitz, Jeremy and Wiggins, Jeffrey, Polymer Degradation and Stability 2016, 125, 76 iv. High Molecular Weight and Low Dispersity... Applications Jessica Piness, Katrina Knauer, Jeffrey Wiggins, SAMPE Tech 2015, Baltimore, MD, May 2015 xxvi. Cure behavior and polymer chain dynamics of

  18. Development of novel multifunctional biobased polymer composites with tailored conductive network of micro-and-nano-fillers

    NASA Astrophysics Data System (ADS)

    Leung, Siu N.; Ghaffari, Shahriar; Naguib, Hani E.

    2013-04-01

    Biobased/green polymers and nanotechnology warrant a multidisciplinary approach to promote the development of the next generation of materials, products, and processes that are environmentally sustainable. The scientific challenge is to find the suitable applications, and thereby to create the demand for large scale production of biobased/green polymers that would foster sustainable development of these eco-friendly materials in contrast to their petroleum/fossil fuel derived counterparts. In this context, this research aims to investigate the synergistic effect of green materials and nanotechnology to develop a new family of multifunctional biobased polymer composites with promoted thermal conductivity. For instance, such composite can be used as a heat management material in the electronics industry. A series of parametric studies were conducted to elucidate the science behind materials behavior and their structure-toproperty relationships. Using biobased polymers (e.g., polylactic acid (PLA)) as the matrix, heat transfer networks were developed and structured by embedding hexagonal boron nitride (hBN) and graphene nanoplatelets (GNP) in the PLA matrix. The use of hybrid filler system, with optimized material formulation, was found to promote the composite's effective thermal conductivity by 10-folded over neat PLA. This was achieved by promoting the development of an interconnected thermally conductive network through structuring hybrid fillers. The thermally conductive composite is expected to afford unique opportunities to injection mold three-dimensional, net-shape, lightweight, and eco-friendly microelectronic enclosures with superior heat dissipation performance.

  19. The first water-soluble pillar[5]arene dimer: synthesis and construction of a reversible fluorescent supramolecular polymer network in water.

    PubMed

    Sun, Yan; Wang, Jin; Yao, Yong

    2016-12-20

    The first water-soluble pillar[n]arene (n = 5) dimer was successfully synthesized. This dimer can complex with carboxylate anion-functionalized tetraphenyl ethylene to form a reversible fluorescent supramolecular polymer network in water.

  20. From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

    PubMed

    Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

    2008-10-08

    High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

  1. Characterization of nanocellulose reinforced semi-interpenetrating polymer network of poly(vinyl alcohol) & polyacrylamide composite films.

    PubMed

    Mandal, Arup; Chakrabarty, Debabrata

    2015-12-10

    Semi-interpenetrating polymer network (semi-IPN) of poly(vinyl alcohol)/polyacrylamide was reinforced with various doses of nanocellulose. The different composite films thus prepared were characterized with respect to their mechanical, thermal, morphological and barrier properties. The composite film containing 5 wt.% of nanocellulose showed the highest tensile strength. The semi-interpenetrating polymer network of poly(vinyl alcohol)/polyacrylamide; and its various composites with nanocellulose were almost identical in their thermal stability. Each of the composites however exhibited much superior stability with respect to the linear poly(vinyl alcohol) and crosslinked polyacrylamide. The scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies exhibited phase separated morphology where agglomerates of nanocellulose were found to be dispersed in the matrix of the semi-IPN. The moisture vapor transmission rate (MVTR) was the lowest for the film containing 5 wt.% of nanocellulose.

  2. Hydrogel based on interpenetrating polymer networks of dextran and gelatin for vascular tissue engineering.

    PubMed

    Liu, Yunxiao; Chan-Park, Mary B

    2009-01-01

    Hydrogel networks are highly desirable as three-dimensional (3-D) tissue engineering scaffolds for cell encapsulation due to the high water content and ability to mimick the native extracellular matrix. However, their application is limited by their nanometer-scale mesh size, which restricts the spreading and proliferation of encapsulated cells, and their poor mechanical properties. This study seeks to address both limitations through application of a novel cell-encapsulating hydrogel family based on the interpenetrating polymer network (IPN) of gelatin and dextran bifunctionalized with methacrylate (MA) and aldehyde (AD) (Dex-MA-AD). The chemical structure of the synthesized Dex-MA-AD was verified by (1)H-NMR and the degrees of substitution of MA and AD were found to be 14 and 13.9+/-1.3 respectively. The water contents in all these hydrogels were approximately 80%. Addition of 40 mg/ml to 60 mg/ml gelatin to neat Dex-MA-AD increased the compressive modulus from 15.4+/-3.0 kPa to around 51.9+/-0.1 kPa (about 3.4-fold). Further, our IPN hydrogels have higher dynamic storage moduli (i.e. on the order of 10(4)Pa) than polyethylene glycol-based hydrogels (around 10(2)-10(3)Pa) commonly used for smooth muscle cells (SMCs) encapsulation. Our dextran-based IPN hydrogels not only supported endothelial cells (ECs) adhesion and spreading on the surface, but also allowed encapsulated SMCs to proliferate and spread in the bulk interior of the hydrogel. These IPN hydrogels appear promising as 3-D scaffolds for vascular tissue engineering.

  3. Insight into the crystallization of amorphous imine-linked polymer networks to 2D covalent organic frameworks.

    PubMed

    Smith, Brian J; Overholts, Anna C; Hwang, Nicky; Dichtel, William R

    2016-03-04

    We explore the crystallization of a high surface area imine-linked two-dimensional covalent organic framework (2D COF). The growth process reveals rapid initial formation of an amorphous network that subsequently crystallizes into the layered 2D network. The metastable amorphous polymer may be isolated and resubjected to growth conditions to form the COF. These experiments provide the first mechanistic insight into the mechanism of imine-linked 2D COF formation, which is distinct from that of boronate-ester linked COFs.

  4. Deducing nanopore structure and growth mechanisms in porogen-templated silsesquioxane thin films

    NASA Astrophysics Data System (ADS)

    Peng, Hua-Gen; Vallery, Richard S.; Liu, Ming; Frieze, William E.; Gidley, David W.; Yim, Jin-Heong; Jeong, Hyun-Dam; Kim, Jongmin

    2005-10-01

    Adjusting the functional group of a porogen is found to have a tremendous effect on the pore structre of porous low dielectric constant films with silsesquioxane as the matrix precursor. The pore size and interconnection length measured by positronium annihilation lifetime spectroscopy can be used to deduce the pore shape and its evolution with porosity from templates of isolated porogen molecules through film percolation. Inert, self-linkable, and amphiphilic porogens are demonstrated to randomly aggregate three-dimensionally, linearly polymerize, and form micelles, respectively.

  5. Morphological Behavior of Thin Polyhedral Oligomeric Silsesquioxane Films at the Molecular Scale

    SciTech Connect

    G Evmenenko; B Stripe; P Dutta

    2011-12-31

    Synchrotron X-ray reflectivity (XRR) was used to study the structure of thin films of polyhedral oligomeric silsesquioxanes (POSS) with side organic chains of different flexibility and containing terminal epoxy groups. POSS films were deposited from volatile solvents on hydroxylated and hydrogen-passivated silicon surfaces. The XRR data show a variety of structural morphologies, including autophobic molecular monolayers and bilayers as well as uniform films. The role of conformational and energetic factors governing the development of different morphologies in a restricted geometry is discussed.

  6. Biodegradation study of enzymatically catalyzed interpenetrating polymer network: Evaluation of agrochemical release and impact on soil fertility.

    PubMed

    Saruchi; Kaith, B S; Kumar, Vaneet; Jindal, R

    2016-03-01

    A novel interpenetrating polymer network (IPN) has been synthesized through enzymatic initiation using lipase as initiator, glutaraldehyde as cross-linker, acrylic acid as primary monomer and acrylamide as secondary monomer. Biodegradability of synthesized interpenetrating polymer network was studied through soil burial and composting methods. Synthesized hydrogel was completely degraded within 70 days using composting method, while it was 86.03% degraded within 77 days using soil burial method. This was confirmed by Fourier transform Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) techniques. Synthesized interpenetrating polymer network hydrogel was used as a device for controlled release of urea and also act as water releasing device. Their impact on soil fertility and plant growth was also studied. The initial diffusion coefficient has a greater value than the later diffusion coefficient indicating a higher fertilizer release rate during the early stage. Fertilizer release kinetic was also studied which showed Non-Fickian diffusion behavior, as the rate of fertilizer release was comparable to the relaxation time of the synthesized matrix. Synthesized IPN enhance the water uptake capacity up to 6.2% and 7.2% in sandy loam and clay soil, respectively.

  7. Regulation Mechanism of Salt Ions for Superlubricity of Hydrophilic Polymer Cross-Linked Networks on Ti6Al4V.

    PubMed

    Zhang, Caixia; Liu, Yuhong; Liu, Zhifeng; Zhang, Hongyu; Cheng, Qiang; Yang, Congbin

    2017-03-07

    Poly(vinylphosphonic acid) (PVPA) cross-linked networks on Ti6Al4V show superlubricity behavior when sliding against polytetrafluoroethylene in water-based lubricants. The superlubricity can occur but only with the existence of salt ions in the polymer cross-linked networks. This is different from the phenomenon in most polymer brushes. An investigation into the mechanism revealed that cations and anions in the lubricants worked together to yield the superlubricity even under harsh conditions. It is proposed that the preferential interactions of cations with PVPA molecules rather than water molecules are the main reason for the superlubricity in water-based lubricants. The interaction of anions with water molecules regulates the properties of the tribological interfaces, which influences the magnitude of the friction coefficient. Owing to the novel cross-linked networks and the interactions between cations and polymer molecules, their superlubricity can be maintained even at a high salt ion concentration of 5 M. These excellent properties make PVPA-modified Ti6Al4V a potential candidate for application in artificial implants.

  8. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

    SciTech Connect

    Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto; Adroher-Benítez, Irene

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated.

  9. Semi-interpenetrating polymer network proton exchange membranes with narrow and well-connected hydrophilic channels

    NASA Astrophysics Data System (ADS)

    Fang, Chunliu; Toh, Xin Ni; Yao, Qiaofeng; Julius, David; Hong, Liang; Lee, Jim Yang

    2013-03-01

    Four series of semi-interpenetrating polymer network (SIPN) membranes are fabricated by thermally cross-linking aminated BPPO (brominated poly(2,6-dimethyl-1,4-phenylene oxide)) with different epoxide cross-linkers in the presence of sulfonated PPO (SPPO). The cross-link structure and hydrophobicity are found to impact the membrane morphology strongly - smaller and more hydrophobic cross-links form narrow and well-connected hydrophilic channels whereas bulky and less hydrophobic cross-links form wide but less-connected hydrophilic channels. The membranes of the former can support facile proton transport and suppress methanol crossover to result in higher proton conductivity and lower methanol permeability than the membranes of the latter. The membranes are also fabricated into membrane electrode assemblies (MEAs) and tested in single-stack direct methanol fuel cells (DMFCs). It is found that some of these SIPN membranes can surpass Nafion® 117 in maximum power density, demonstrating their potential as a proton exchange membrane (PEM) for the DMFCs.

  10. Investigation of the growth mechanisms of diglyme plasma polymers on amyloid fibril networks

    NASA Astrophysics Data System (ADS)

    Li, Yali; Reynolds, Nicholas P.; Styan, Katie E.; Muir, Benjamin W.; Forsythe, John S.; Easton, Christopher D.

    2016-01-01

    Within the area of biomaterials research, the ability to tailor a materials surface chemistry while presenting a biomimetic topography is a useful tool for studying cell-surface and cell-cell interactions. For the study reported here we investigated the deposition of diglyme plasma polymer films (DGpp) onto amyloid fibril networks (AFNs), which have morphologies that mimic the extracellular matrix. We extend our previous work to observe that the nanoscale contours of the AFNs are well preserved even under thick layers of DGpp. The width of the surface features is positively correlated to the DGpp thickness. DGpp film growth conformed to the underlying fibril features, with a gradual smoothing out of the resultant surface topography. Further, to understand how the films grow on top of AFNs, X-ray photoelectron spectroscopy depth profiling was employed to determine the elemental composition within the coating, perpendicular to the plane of the substrate. It was found that AFNs partially fragment during the initial stage of plasma polymerisation, and these fragments then mix with the growing DGpp to form an intermixed interface region above the AFN. The findings in this study are likely applicable to situations where plasma polymerisation is used to apply an overcoat to adsorbed organic and/or biological molecules.

  11. Direct induction of molecular alignment in liquid crystal polymer network film by photopolymerization

    NASA Astrophysics Data System (ADS)

    Hisano, K.; Aizawa, M.; Ishizu, M.; Kurata, Y.; Shishido, A.

    2016-09-01

    Liquid crystal (LC) is the promising material for the fabrication of high-performance soft, flexible devices. The fascinating and useful properties arise from their cooperative effect that inherently allows the macroscopic integration and control of molecular alignment through various external stimuli. To date, light-matter interaction is the most attractive stimuli and researchers developed photoalignment through photochemical or photophysical reactions triggered by linearly polarized light. Here we show the new choice based on molecular diffusion by photopolymerization. We found that photopolymerization of a LC monomer and a crosslinker through a photomask enables to direct molecular alignment in the resultant LC polymer network film. The key generating the molecular alignment is molecular diffusion due to the difference of chemical potentials between irradiated and unirradiated regions. This concept is applicable to various shapes of photomask and two-dimensional molecular alignments can be fabricated depending on the spatial design of photomask. By virtue of the inherent versatility of molecular diffusion in materials, the process would shed light on the fabrication of various high-performance flexible materials with molecular alignment having controlled patterns.

  12. In vivo dynamical behavior of yeast chromatin modeled as an entangled polymer network with constraint release

    NASA Astrophysics Data System (ADS)

    Wang, Chenxi; Kilfoil, Maria L.

    2013-03-01

    The high fidelity segregation of chromatin is the central problem in cell mitosis. The role of mechanics underlying this, however, is undetermined. Work in this area has largely focused on cytoskeletal elements of the process. Preliminary work in our lab suggests the mechanical properties of chromatin are fundamental in this process. Nevertheless, the mechanical properties of chromatin in the cellular context are not well-characterized. For better understanding of the role of mechanics in this cellular process, and of the chromatin mechanics in vivo generally, a systematic dynamical description of chromatin in vivo is required. Accordingly, we label specific sites on chromatin with fluorescent proteins of different wave lengths, enabling us to detect multiple spots separately in 3D and track their displacements in time inside living yeast cells. We analyze the pairwise cross-correlated motion between spots as a function of relative distance along the DNA contour. Comparison between the reptation model and our data serves to test our conjecture that chromatin in the cell is basically an entangled polymer network under constraints to thermal motion, and removal of constraints by non-thermal cellular processes is expected to affect its dynamic behavior.

  13. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: a Monte Carlo simulation study.

    PubMed

    Quesada-Pérez, Manuel; Adroher-Benítez, Irene; Maroto-Centeno, José Alberto

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated.

  14. Controlling Phase Separation of Tough Interpenetrating Polymer Networks via Addition of Amphiphilic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Rohde, Brian; Krishnamoorti, Ramanan; Robertson, Megan

    Interpenetrating polymer networks (IPNs) offer a unique way to combine the mechanical properties of two thermoset systems. Often used to create a material that possesses both high toughness and tensile properties, here we use polydicyclopentadiene, cured via ring opening metathesis polymerization, to contribute high toughness and diglycidyl ether of bisphenol A cured via anhydride chemistry to contribute high tensile strength and modulus. As the uncompatibilized system reacts in the presence of one another, mesoscopic phase separation occurs and dictates the overall efficacy of combining mechanical properties. To control phase separation and drive the system towards more mechanically robust nanostructed IPNs, amphiphilic block copolymers of polybutadiene- b-polyethylene oxide, where one block possesses strong affinity to polyDCPD and the other the DGEBA, were added to the system. Here we present a systematic study of the influence of block copolymer composition in the overall blend on degree of phase separation and morphology using a combination of small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) techniques. The resultant mechanical properties are then explored in an effort to link mechanical properties to blend morphology.

  15. Highly sensitive gas-phase explosive detection by luminescent microporous polymer networks

    PubMed Central

    Räupke, André; Palma-Cando, Alex; Shkura, Eugen; Teckhausen, Peter; Polywka, Andreas; Görrn, Patrick; Scherf, Ullrich; Riedl, Thomas

    2016-01-01

    We propose microporous networks (MPNs) of a light emitting spiro-carbazole based polymer (PSpCz) as luminescent sensor for nitro-aromatic compounds. The MPNs used in this study can be easily synthesized on arbitrarily sized/shaped substrates by simple and low-cost electrochemical deposition. The resulting MPN afford an extremely high specific surface area of 1300 m2/g, more than three orders of magnitude higher than that of the thin films of the respective monomer. We demonstrate, that the luminescence of PSpCz is selectively quenched by nitro-aromatic analytes, e.g. nitrobenzene, 2,4-DNT and TNT. In striking contrast to a control sample based on non-porous spiro-carbazole, which does not show any luminescence quenching upon exposure to TNT at levels of 3 ppm and below, the microporous PSpCz shows a clearly detectable response even at TNT concentrations as low as 5 ppb, clearly demonstrating the advantage of microporous films as luminescent sensors for traces of explosive analytes. This level states the vapor pressure of TNT at room temperature. PMID:27373905

  16. Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Based Monomers and Polymers

    DTIC Science & Technology

    2011-07-19

    for use a building block material for low surface energy materials • Applications – Mechanical robust superhydrophobic /oleophobic/omniphobic surfaces...modifiers, and many other applications Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chem. Rev. 2010, 110, 2081. Phillips, S. H.; Haddad, T. S.; Tomczak...surface energies leading to the creation of superhydrophobic and oleophobic surfaces. (a) Mabry, J. M.; Vij, A.; Iacono, S. T.; Viers, b. D., Angew

  17. Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Based Monomers and Polymers

    DTIC Science & Technology

    2011-04-04

    potential applications in su perhydrophobic/oleophobic coatings and low-surface energy materials. Experimental Materials. All dichlor osilanes wer...copoly mer via f ree radical polymerization. These novel structures can be used in the development of new superhydrophobic and oleophobic materials

  18. Polymer Optical Fiber Sensor and the Prediction of Sensor Response Utilizing Artificial Neural Networks

    NASA Astrophysics Data System (ADS)

    Haroglu, Derya

    characteristics: reproducibility, accuracy, selectivity, aging, and resolution. Artificial neural network (ANN), a mathematical model formed by mimicking the human nervous system, was used to predict the sensor response. Qwiknet (version 2.23) software was used to develop ANNs and according to the results of Qwiknet the prediction performances for training and testing data sets were 75%, and 83.33% respectively. In this dissertation, Chapter 1 describes the worldwide plastic optical fiber (POF) and fiber optic sensor markets, and the existing textile structures used in fiber optic sensing design particularly for the applications of biomedical and structural health monitoring (SHM). Chapter 2 provides a literature review in detail on polymer optical fibers, fiber optic sensors, and occupancy sensing in the passenger seats of automobiles. Chapter 3 includes the research objectives. Chapter 4 presents the response of POF to tensile loading, bending, and cyclic tensile loading with discussion parts. Chapter 5 includes an e-mail based survey to prioritize customer needs in a Quality Function Deployment (QFD) format utilizing Analytic Hierarchy Process (AHP) and survey results. Chapter 6 describes the POF sensor design and the behavior of it under pressure. Chapter 7 provides a data analysis based on the experimental results of Chapter 6. Chapter 8 presents the summary of this study and recommendations for future work.

  19. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

    PubMed Central

    Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

    2015-01-01

    In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g−1) and large pore volumes (up to 0.90 cm3 g−1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4′-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405−; the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane. PMID:26062725

  20. Synthesis and characterization of magnetic carbon nanotubes/silsesquioxane nanocomposite thin films

    NASA Astrophysics Data System (ADS)

    Osorio, Alice Gonçalves; Machado, Geraldo Beyer; Pereira, Marcelo Barbalho; Benvenutti, Edilson Valmir; Pereira, Luis Gustavo; Bergmann, Carlos Perez; Oliveira, Artur Harres de; Costa, Tania Maria Haas

    2016-05-01

    In the present study, magnetic carbon nanotubes (CNTs)/silsesquioxane nanocomposites were produced by sol-gel method and deposited as thin film by dip-coating process. Blank films and films with CNTs were characterized in order to evaluate their chemical composition and morphology. Profilometry technique showed the formation of films with 305 ± 22 nm of thickness for blank samples (without CNTs) and 173 ± 05 nm thickness for samples with CNTs. Microscopy techniques indicated the presence of CNTs well dispersed in the films and, with the aid of Raman and Fourier Transform Infrared spectroscopy, chemical composition of silsesquioxane matrix was evidenced and the presence of CNTs was confirmed in the films. Finally, the magnetic response of the deposited films was analyzed by Alternating Gradient-Field Magnetometer and results indicated that films reinforced with CNTs showed a hysteresis loop that indicates a coercivity of 103 Oe and the blank film did not show any significant response to the field applied. Hence, the authors suggest that this hybrid organic-inorganic material has potential to be applied as a new material for magnetic storage.

  1. Superplastic behavior of silica nanowires obtained by direct patterning of silsesquioxane-based precursors.

    PubMed

    Yılmaz, Mustafa; Wollschläger, Nicole; Esfahani, Mohammad Nasr; Österle, Werner; Leblebici, Yusuf; Alaca, B Erdem

    2017-03-17

    Silica nanowires spanning 10 μm-deep trenches are fabricated from different types of silsesquioxane-based precursors by direct e-beam patterning on silicon followed by release through deep reactive ion etching. Nanowire aspect ratios as large as 150 are achieved with a critical dimension of about 50 nm and nearly rectangular cross-sections. In situ bending tests are carried out inside a scanning electron microscope, where the etch depth of 10 [Formula: see text] provides sufficient space for deformation. Silica NWs are indeed observed to exhibit superplastic behavior without fracture with deflections reaching the full etch depth, about two orders of magnitude larger than the nanowire thickness. A large-deformation elastic bending model is utilized for predicting the deviation from the elastic behavior. The results of forty different tests indicate a critical stress level of 0.1-0.4 GPa for the onset of plasticity. The study hints at the possibility of fabricating silica nanowires in a monolithic fashion through direct e-beam patterning of silsesquioxane-based resins. The fabrication technology is compatible with semiconductor manufacturing and provides silica nanowires with a very good structural integrity.

  2. Superplastic behavior of silica nanowires obtained by direct patterning of silsesquioxane-based precursors

    NASA Astrophysics Data System (ADS)

    Yılmaz, Mustafa; Wollschläger, Nicole; Nasr Esfahani, Mohammad; Österle, Werner; Leblebici, Yusuf; Erdem Alaca, B.

    2017-03-01

    Silica nanowires spanning 10 μm-deep trenches are fabricated from different types of silsesquioxane-based precursors by direct e-beam patterning on silicon followed by release through deep reactive ion etching. Nanowire aspect ratios as large as 150 are achieved with a critical dimension of about 50 nm and nearly rectangular cross-sections. In situ bending tests are carried out inside a scanning electron microscope, where the etch depth of 10 μ {{m}} provides sufficient space for deformation. Silica NWs are indeed observed to exhibit superplastic behavior without fracture with deflections reaching the full etch depth, about two orders of magnitude larger than the nanowire thickness. A large-deformation elastic bending model is utilized for predicting the deviation from the elastic behavior. The results of forty different tests indicate a critical stress level of 0.1–0.4 GPa for the onset of plasticity. The study hints at the possibility of fabricating silica nanowires in a monolithic fashion through direct e-beam patterning of silsesquioxane-based resins. The fabrication technology is compatible with semiconductor manufacturing and provides silica nanowires with a very good structural integrity.

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

    PubMed

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

    2014-01-14

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

  4. Interpenetrating polymer networks of poly(N-vinylacetamide) and stimuli responsive polymers applied to novel amphiphilic gel.

    PubMed

    Ajiro, Hiroharu; Takemoto, Yukie; Akashi, Mitsuru

    2011-08-01

    The swelling behaviors of IPN with poly(N-vinylacetamide) (PNVA), which possibly converts from nonionic gel to cationic gel, and the stimuli responsive polymers, such as poly(acrylic acid) (PAAc) and poly(N-isopropylacrylamide) (PNIPAm) were investigated in order to prepare the stimuli responsive amphiphilic gel. When the monomer concentrations were uniformed at the IPN preparation, the obtained PNVA/PAAc IPN showed the pH responsivity with around 100 of swelling ratio at pH 4 to around 1 of swelling ratio at pH 2, although it lost the amphiphilicity due to the lack of swelling in ethanol. On the other hand, the gelation of N-vinylacetamide at 2 M in PNIPAM gel resulted in thermosensitive and amphiphilic hydrogel, that the swelling ratio in EtOH/water (3/7, v/v) also decreased, compared to the value in water at 25 degrees C.

  5. Thermo-reversible morphology and conductivity of a conjugated polymer network embedded in polymeric self-assembly

    NASA Astrophysics Data System (ADS)

    Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; Li, Yunchao; Hong, Kunlun; Sumpter, Bobby G.; Ohl, Michael; Paranthaman, Mariappan Parans; Smith, Gregory S.; Do, Changwoo

    Self-assembly of block copolymers provides opportunities to create nano hybrid materials, utilizing self-assembled micro-domains with a variety of morphology and periodic architectures as templates for functional nano-fillers. Here we report new progress towards the fabrication of a thermally responsive conducting polymer self-assembly made from a water-soluble poly(thiophene) derivative with short PEO side chains and Pluronic L62 solution in water. The structural and electrical properties of conjugated polymer-embedded nanostructures were investigated by combining SANS, SAXS, CGMD simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. The conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. The research was sponsored by the Scientific User Facilities Division, Office of BES, U.S. DOE and Laboratory Directed Research and Development Program of ORNL, managed by UT-Battelle, LLC.

  6. Modeling of an ionic polymer metal composite actuator based on an extended Kalman filter trained neural network

    NASA Astrophysics Data System (ADS)

    Quang Truong, Dinh; Ahn, Kyoung Kwan

    2014-07-01

    An ion polymer metal composite (IPMC) is an electroactive polymer that bends in response to a small applied electric field as a result of mobility of cations in the polymer network and vice versa. This paper presents an innovative and accurate nonlinear black-box model (NBBM) for estimating the bending behavior of IPMC actuators. The model is constructed via a general multilayer perceptron neural network (GMLPNN) integrated with a smart learning mechanism (SLM) that is based on an extended Kalman filter with self-decoupling ability (SDEKF). Here the GMLPNN is built with an ability to autoadjust its structure based on its characteristic vector. Furthermore, by using the SLM based on the SDEKF, the GMLPNN parameters are optimized with small computational effort, and the modeling accuracy is improved. An apparatus employing an IPMC actuator is first set up to investigate the IPMC characteristics and to generate the data for training and validating the model. The advanced NBBM model for the IPMC system is then created with the proper inputs to estimate IPMC tip displacement. Next, the model is optimized using the SLM mechanism with the training data. Finally, the optimized NBBM model is verified with the validating data. A comparison between this model and the previously developed model is also carried out to prove the effectiveness of the proposed modeling technique.

  7. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network

    PubMed Central

    Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu

    2014-01-01

    Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers. PMID:25296246

  8. Evaluation of semi-interpenetrating polymer networks composed of chitosan and poloxamer for wound dressing application.

    PubMed

    Kim, I Y; Yoo, M K; Seo, J H; Park, S S; Na, H S; Lee, H C; Kim, S K; Cho, C S

    2007-08-16

    We have elsewhere reported the work on the preparation of semi-interpenetrating polymer networks (SIPNs) composed of chitosan (CS) and poloxamer to improve the mechanical strength of CS sponge. This study focuses on evaluation of the CS/poloxamer SIPNs to intend for wound dressing application and the efficacy of dehydroepiandrosterone (DHEA)-loaded CS/poloxamer SIPNs in the wound model studies. The properties required for ideal wound dressing, such as equilibrium water content (EWC), water absorption (A(w)), water vapor transmission rate (WVTR), and evaporative water loss, were examined. The CS/poloxamer SIPNs were found to have a water content of 90% of their weight which could prevent the wound bed from accumulation of exudates and also have excellent water adsorption. The WVTR of CS/poloxamer SIPNs was found to be 2,508.2+/-65.7gm(-2)day(-1), indicating that the SIPNs can maintain a moist environment over wound bed in moderate to heavily exuding wound which enhances epithelial cell migration during the healing process. Also, the CS/poloxamer SIPNs in vitro assessment showed proper biodegradation and low cytotoxicity for wound dressing application. The wound healing efficacy of CS/poloxamer SIPNs as a wound dressing was evaluated on experimental full thickness wounds in a mouse model. It was found that the wounds covered with CS/poloxamer SIPNs or DHEA-loaded CS/poloxamer SIPNs were completely filled with new epithelium without any significant adverse reactions after 3 weeks. The results thus indicate that CS/poloxamer SIPNs could be employed in the future as potential wound dressing materials.

  9. Tracer diffusion in a polymer gel: simulations of static and dynamic 3D networks using spherical boundary conditions.

    PubMed

    Kamerlin, Natasha; Elvingson, Christer

    2016-11-30

    We have investigated an alternative to the standard periodic boundary conditions for simulating the diffusion of tracer particles in a polymer gel by performing Brownian dynamics simulations using spherical boundary conditions. The gel network is constructed by randomly distributing tetravalent cross-linking nodes and connecting nearest pairs. The final gel structure is characterised by the radial distribution functions, chain lengths and end-to-end distances, and the pore size distribution. We have looked at the diffusion of tracer particles with a wide range of sizes, diffusing in both static and dynamic networks of two different volume fractions. It is quantitatively shown that the dynamical effect of the network becomes more important in facilitating the diffusional transport for larger particle sizes, and that one obtains a finite diffusion also for particle sizes well above the maximum in the pore size distribution.

  10. Computational analysis of cartilage implants based on an interpenetrated polymer network for tissue repairing.

    PubMed

    Manzano, Sara; Poveda-Reyes, Sara; Ferrer, Gloria Gallego; Ochoa, Ignacio; Hamdy Doweidar, Mohamed

    2014-10-01

    Interpenetrated polymer networks (IPNs), composed by two independent polymeric networks that spatially interpenetrate, are considered as valuable systems to control permeability and mechanical properties of hydrogels for biomedical applications. Specifically, poly(ethyl acrylate) (PEA)-poly(2-hydroxyethyl acrylate) (PHEA) IPNs have been explored as good hydrogels for mimicking articular cartilage. These lattices are proposed as matrix implants in cartilage damaged areas to avoid the discontinuity in flow uptake preventing its deterioration. The permeability of these implants is a key parameter that influences their success, by affecting oxygen and nutrient transport and removing cellular waste products to healthy cartilage. Experimental try-and-error approaches are mostly used to optimize the composition of such structures. However, computational simulation may offer a more exhaustive tool to test and screen out biomaterials mimicking cartilage, avoiding expensive and time-consuming experimental tests. An accurate and efficient prediction of material's permeability and internal directionality and magnitude of the fluid flow could be highly useful when optimizing biomaterials design processes. Here we present a 3D computational model based on Sussman-Bathe hyperelastic material behaviour. A fluid structure analysis is performed with ADINA software, considering these materials as two phases composites where the solid part is saturated by the fluid. The model is able to simulate the behaviour of three non-biodegradable hydrogel compositions, where percentages of PEA and PHEA are varied. Specifically, the aim of this study is (i) to verify the validity of the Sussman-Bathe material model to simulate the response of the PEA-PHEA biomaterials; (ii) to predict the fluid flux and the permeability of the proposed IPN hydrogels and (iii) to study the material domains where the passage of nutrients and cellular waste products is reduced leading to an inadequate flux

  11. Strontium-containing, carbohydrate-based polymer networks as tooth-adherent systems for the treatment of dentine hypersensitivity.

    PubMed

    Jones, Dary K F; Andrews, Gavin P; Jones, David S

    2017-02-10

    This study describes the design/physicochemical properties of strontium-containing, mucoadhesive carbohydrate polymeric platforms, designed as treatments for dentine hypersensitivity. Interactive networks were composed of strontium chloride (10% w/w), one of two base polymers (sodium carboxymethylcellulose, NaCMC or hydroxyethylcellulose, HEC), polycarbophil (PC) and, when required, polyvinylpyrrolidone (PVP). The physicochemical properties were characterised using oscillatory and flow rheometry, texture profile analysis, mucoadhesion analysis and, additionally, the strontium release properties were examined. All platforms exhibited pseudoplastic flow. Increasing polymer concentrations increased network viscoelasticity, consistency, hardness, compressibility, gel strength, adhesiveness, mucoadhesion and, retarded strontium release. Principally zero-order strontium release was observed from all platforms. Incorporation of strontium reduced the network elasticity, consistency, hardness, compressibility, gel strength and mucoadhesion; HEC-based platforms being affected to a greater extent than NaCMC platforms. NaCMC-based platforms containing 10% strontium chloride, PVP (3% w/w) and PC (3% w/w) potentially displayed the correct balance of physicochemical properties for the treatment of dentine sensitivity.

  12. Modification of Polymer Network Properties through the Addition of Functional Nanogel Particles

    NASA Astrophysics Data System (ADS)

    Liu, JianCheng

    Multifunctional acrylic and methacrylic monomers have been widely applied in many photopolymerization applications to produce crosslinked polymers with advantages such as rapid curing, broad choices of commercially available monomers and desirable physical and mechanical properties. However, there still remain critical challenges for these materials during polymerization including limited conversion and early onset of gelation as well as the generation of significant polymerization shrinkage and stress. This thesis explores the effects of network property modification through the addition of polymeric nanoparticles or nanogels. In order to understand the relationship between nanogel structure and composite material properties, nanogels with different architectures and functionalities were studied during polymerization in terms of kinetics, shrinkage and stress reduction, mechanical performance and reaction mechanisms. Nanogel composite formulations were evaluated to understand the interaction between nanogel structure with the resin matrix during polymerization through adjustment of nanogel branching densities and reactivity of polymer chain ends. It was found that both the chemical crosslinking from reactive chain ends and physical entanglements of high branching density nanogels with the resin matrix dramatically could improve final material mechanical strength. The reductions in overall volumetric shrinkage and shrinkage stress were found to follow at least proportional behavior with respect to nanogel loading concentration while maintaining similar final conversion and modulus results compared with the control resin. Nanogels containing unique functionalities were designed in order to modify reaction mechanism during secondary polymerization. A nanogel containing an integrated photoinitiator and active chain-end RAFT groups was able to initiate secondary polymerization from the nanogel phase so that localized polymerization was achieved from the beginning of

  13. Computational molecular design of polyhedral oligomeric silsesquioxane based organic-inorganic hybrid semiconductors

    NASA Astrophysics Data System (ADS)

    Qi, Feng

    Cubic silsesquioxanes (T8 SQs), with the formula of [RSiO1.5] 8, enable advanced materials design. In this thesis, a computational materials science framework, including ab initio density functional theory (DFT) calculations, molecular dynamics (MD), and Monte Carlo (MC) simulations, was developed to perform computational molecular design and crystal engineering of silsesquioxane based diacene-SQ and then octa(halogenphenyl)-SQ molecular systems. The goal of this project was to identify novel molecular architectures, a priori, that exhibit targeted self-assembly behaviors and result in materials with improved electronic properties. First, existing force fields, including our in house charge transfer reactive (CTR) force field, and COMPASS, were evaluated for simulating cubic silsesquioxane systems. All force fields reproduced the experimental structure of SQ-based crystals very well. However, only the FLX force field reproduced the experimentally observed vibrational properties and thermodynamic behavior. Next, targeting materials performance, such as high electronic mobility, a series of diacene-SQ molecules were designed and their crystal structures predicted by following the computational molecular design recipe that accounts for transport theory, symmetry relationships, polymorph prediction procedures, and solid state electronic property evaluation methods. Computationally derived diacene-SQ crystals are predicted to exhibit advanced electronic properties, such as very small band gaps and parallel packing of the acene groups in crystal structures, indicating excellent transport properties, as well as improved thermal and mechanical properties. Finally, a series of new small-band gap octa(halogenphenyl)-SQ molecular systems were identified by computationally exploring alternative architectures and functionalization of recently synthesized octa(halogenphenyl)-SQ crystals. These hybrid molecular crystals also feature other unique properties, such as solution

  14. Preparation and Characterization of Polyhedral Oligomeric Silsesquioxane-Containing, Titania-Thiol-Ene Composite Photocatalytic Coatings, Emphasizing the Hydrophobic-Hydrophilic Transition.

    PubMed

    Jefferson, LaCrissia U; Netchaev, Anton D; Jefcoat, Jennifer A; Windham, Amber D; McFarland, Frederick M; Guo, Song; Buchanan, Randy K; Buchanan, J Paige

    2015-06-17

    Coatings prepared from titania-thiol-ene compositions were found to be both self-cleaning, as measured by changes in water contact angle, and photocatalytic toward the degradation of an organic dye. Stable titania-thiol-ene dispersions at approximately 2 wt % solids were prepared using a combination of high-shear mixing and sonication in acetone solvent from photocatalytic titania, trisilanol isobutyl polyhedral oligomeric silsesquioxane (POSS) dispersant, and select thiol-ene monomers, i.e., trimethylolpropane tris(3-mercaptopropionate) (TMPMP), pentaerythritol allyl ether (APE), and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). The dispersed particle compositions were characterized by DLS and TEM. The synthetic methods employed yield a strongly bound particle/POSS complex, supported by IR, 29Si NMR, and TGA. The factors of spray techniques, carrier solvent volatility, and particle size and size distributions, in combination, likely all contribute to the highly textured but uniform surfaces observed via SEM and AFM. Polymer composites possessed thermal transitions (e.g., Tg) consistent with composition. In general, the presence of polymer matrix provided mechanical integrity, without significantly compromising or prohibiting other critical performance characteristics, such as film processing, photocatalytic degradation of adsorbed contaminants, and the hydrophobic-hydrophilic transition. In all cases, coatings containing photocatalytic titania were converted from superhydrophobic to superhydrophilic, as defined by changes in the water contact angle. The superhydrophilic state of samples was considered persistent, since long time durations in complete darkness were required to observe any significant hydrophobic return. In a preliminary demonstration, the photocatalytic activity of prepared coatings was confirmed through the degradation of crystal violet dye. This work demonstrates that a scalable process can be found to prepare titania

  15. Polymer/Carbon Nanotube Networks for Smart, Self-Repairing and Light-Weighted Nanocomposites

    DTIC Science & Technology

    2012-11-05

    was develop smart, strong, and light-weight polymer/carbon nanotube (CNT) composites which will sense tribologically induced damages and self-heal by...light-weight polymer/carbon nanotube (CNT) composites which will sense tribologically induced damages and self-heal by inhibiting such degradation...vol%). This might have been the reason, why we did not observe large difference in mechanical and tribological properties between virgin PS and PS/CNT

  16. Synthesis and gas adsorption properties of tetra-armed microporous organic polymer networks based on triphenylamine.

    PubMed

    Yang, Xiao; Yao, Shuwen; Yu, Miao; Jiang, Jia-Xing

    2014-04-01

    Two novel tetra-armed microporous organic polymers have been designed and synthesized via a nickel-catalyzed Yamamoto-type Ullmann cross-coupling reaction or Suzuki cross-coupling polycondensation. These polymers are stable in various solvents, including concentrated hydrochloric acid, and are thermally stable. The homocoupled polymer YPTPA shows much higher Brunauer-Emmet-Teller-specific surface area up to 1557 m(2) g(-1) than the copolymer SPTPA (544 m(2) g(-1)), and a high CO2 uptake ability of 3.03 mmol g(-1) (1.13 bar/273 K) with a CO2 /N2 sorption selectivity of 17.3:1. Both polymers show high isosteric heats of CO2 adsorption (22.7-26.5 kJ mol(-1)) because the incorporation of nitrogen atoms into the skeleton of microporous organic polymers enhances the interaction between the pore wall and the CO2 molecules. The values are higher than those of the porous aromatic frameworks, which contain neither additional polar functional groups nor nitrogen atoms, and are rather close to those of previously reported microporous organic polymers containing the nitrogen atoms on the pore wall. These data show that these materials would be potential candidates for applications in post-combustion CO2 capture and sequestration technology.

  17. The effect of molecular mobility on electronic transport in carbon nanotube-polymer composites and networks

    SciTech Connect

    Shenogin, Sergei; Lee, Jonghoon; Voevodin, Andrey A.; Roy, Ajit K.

    2014-12-21

    A multiscale modeling approach to the prediction of electrical conductivity in carbon nanotube (CNT)–polymer composite materials is developed, which takes into account thermally activated molecular mobility of the matrix and the CNTs. On molecular level, a tight-binding density functional theory and non-equilibrium Green's function method are used to calculate the static electron transmission function in the contact between two metallic carbon nanotubes that corresponds to electron transport at 0 K. For higher temperatures, the statistical distribution of effective contact resistances is considered that originates from thermal fluctuations of intermolecular distances caused by molecular mobility of carbon nanotube and the polymer matrix. Based on this distribution and using effective medium theory, the temperature dependence of macroscopic electrical resistivity for CNT-polymer composites and CNT mats is calculated. The predicted data indicate that the electrical conductivity of the CNT-polymer composites increases linearly with temperature above 50 K, which is in a quantitative agreement with the experiments. Our model predicts a slight nonlinearity in temperature dependence of electric conductivity at low temperatures for percolated composites with small CNT loading. The model also explains the effect of glass transition and other molecular relaxation processes in the polymer matrix on the composite electrical conductivity. The developed multiscale approach integrates the atomistic charge transport mechanisms in percolated CNT-polymer composites with the macroscopic response and thus enables direct comparison of the prediction with the measurements of macroscopic material properties.

  18. The effect of molecular mobility on electronic transport in carbon nanotube-polymer composites and networks

    NASA Astrophysics Data System (ADS)

    Shenogin, Sergei; Lee, Jonghoon; Voevodin, Andrey A.; Roy, Ajit K.

    2014-12-01

    A multiscale modeling approach to the prediction of electrical conductivity in carbon nanotube (CNT)-polymer composite materials is developed, which takes into account thermally activated molecular mobility of the matrix and the CNTs. On molecular level, a tight-binding density functional theory and non-equilibrium Green's function method are used to calculate the static electron transmission function in the contact between two metallic carbon nanotubes that corresponds to electron transport at 0 K. For higher temperatures, the statistical distribution of effective contact resistances is considered that originates from thermal fluctuations of intermolecular distances caused by molecular mobility of carbon nanotube and the polymer matrix. Based on this distribution and using effective medium theory, the temperature dependence of macroscopic electrical resistivity for CNT-polymer composites and CNT mats is calculated. The predicted data indicate that the electrical conductivity of the CNT-polymer composites increases linearly with temperature above 50 K, which is in a quantitative agreement with the experiments. Our model predicts a slight nonlinearity in temperature dependence of electric conductivity at low temperatures for percolated composites with small CNT loading. The model also explains the effect of glass transition and other molecular relaxation processes in the polymer matrix on the composite electrical conductivity. The developed multiscale approach integrates the atomistic charge transport mechanisms in percolated CNT-polymer composites with the macroscopic response and thus enables direct comparison of the prediction with the measurements of macroscopic material properties.

  19. Conductive network formation of carbon nanotubes in elastic polymer microfibers and its effect on the electrical conductance: Experiment and simulation.

    PubMed

    Cho, Hyun Woo; Kim, Sang Won; Kim, Jeongmin; Kim, Un Jeong; Im, Kyuhyun; Park, Jong-Jin; Sung, Bong June

    2016-05-21

    We investigate how the electrical conductance of microfibers (made of polymers and conductive nanofillers) decreases upon uniaxial deformation by performing both experiments and simulations. Even though various elastic conductors have been developed due to promising applications for deformable electronic devices, the mechanism at a molecular level for electrical conductance change has remained elusive. Previous studies proposed that the decrease in electrical conductance would result from changes in either distances or contact numbers between conductive fillers. In this work, we prepare microfibers of single walled carbon nanotubes (SWCNTs)/polyvinyl alcohol composites and investigate the electrical conductance and the orientation of SWCNTs upon uniaxial deformation. We also perform extensive Monte Carlo simulations, which reproduce experimental results for the relative decrease in conductance and the SWCNTs orientation. We investigate the electrical networks of SWCNTs in microfibers and find that the decrease in the electrical conductance upon uniaxial deformation should be attributed to a subtle change in the topological structure of the electrical network.

  20. Interfacial enhancement of polypropylene composites modified with sorbitol derivatives and siloxane-silsesquioxane resin

    NASA Astrophysics Data System (ADS)

    Dobrzyńska-Mizera, Monika; Dutkiewicz, Michał; Sterzyński, Tomasz; Di Lorenzo, Maria Laura

    2015-12-01

    Composites based on polypropylene (iPP) modified with a sorbitol derivative (NX8000) and siloxane-silsesquioxane resin (SiOPh) containing maleated polypropylene (MAPP) as compatibilizer were prepared by melt extrusion. Calorimetric investigations were carried out using differential scanning calorimetry (DSC), whereas the morphological and mechanical properties were investigated by scanning electron microscopy (SEM) and static tensile tests. DSC measurements revealed no influence of SiOPh and a slight effect of MAPP addition on the crystallization kinetics of polypropylene. Additionally, the introduction of MAPP into the iPP+NX8000+SiOPh composites increased plastic properties of the samples. All the above was attributed to the compatibilizing effect of MAPP which improved interfacial adhesion between iPP, NX8000 and SiOPh. This phenomenon was also confirmed by the SEM images illustrating more homogenous distribution of the filler in the compatibilized samples.

  1. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    PubMed Central

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-01-01

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate. PMID:25687953

  2. Properties of PMR Polyimides Improved by Preparation of Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposites

    NASA Technical Reports Server (NTRS)

    Campbell, Sandi G.; Lee, Andre

    2005-01-01

    The field of hybrid organic-inorganic materials has grown drastically over the last several years. This interest stems from our ever-increasing ability to custom-build and control molecular structure at several length scales. This ability to control both the composition and structure of hybrid materials is sometimes broadly referred to as nanocomposite systems. One class of hybrid (organic-inorganic) nanostructured material is polyhedral oligomeric silsesquioxane (POSS), shown in the preceding diagram. The hybrid composition gives POSS materials dramatically enhanced properties relative to traditional hydrocarbons and inorganics. An important benefit of this technology is that it makes possible the formulations of nanostructured chemicals with excellent thermal and oxidative stability. This is largely due to the inorganic component.

  3. Polyhedral Oligomeric Silsesquioxane Enhances the Brightness of Perovskite Nanocrystal-Based Green Light-Emitting Devices.

    PubMed

    Huang, He; Lin, Hong; Kershaw, Stephen V; Susha, Andrei S; Choy, Wallace C H; Rogach, Andrey L

    2016-11-03

    The beneficial role of the insulating material polyhedral oligomeric silsesquioxane (POSS) as a solution additive or an additional hole-blocking layer to enhance the performance of electroluminescent green light-emitting devices (LEDs) based on CsPbBr3 perovskite nanocrystals is demonstrated. POSS improves the surface coverage and the morphological features of the films deposited either from supernatant or suspension of perovskite nanocrystals. The external quantum efficiency and the luminance efficiency of LEDs with an additional POSS layer reach 0.35% and 1.20 cd/A, respectively, constituting a more than 17-fold enhancement to the reference devices without POSS; the LED peak luminance reaches 2983 cd/m(2), and the device stability is improved. The POSS acts as a hole-blocking layer between the perovskite nanocrystals and TPBi, keeping both electrons and holes located within the active layer for an efficient recombination.

  4. Flow cytometry evidence of human granulocytes interaction with polyhedral oligomeric silsesquioxanes: effect of nanoparticle charge

    NASA Astrophysics Data System (ADS)

    Renò, Filippo; Carniato, Fabio; Rizzi, Manuela; Olivero, Francesco; Pittarella, Pamela; Marchese, Leonardo

    2013-05-01

    Nanoparticles (NPs) entering the human body are immediately confronted with the innate part of human immune system. In particular, monocyte and neutrophil granulocytes readily clear particles by phagocytosis, even if in the case of NPs the uptake mechanism may be classified as macropinocytosis. Among engineered nanoparticles, in the last years, siliceous materials have emerged as promising materials for several applications ranging from catalysis to biomedical. The polyhedral oligomeric silsesquioxanes (POSS) are nanodimensional, easily synthesizable molecular compounds and POSS-based systems are promising carriers for biological molecules. In this work, the ability of human granulocytes to uptake positively and negatively charged POSS was measured using a simple flow cytometry analysis based on cell size modifications. The data obtained showed that after a 30 min exposure only positive NPs were uptaken by human granulocyte using both macropinocytosis and clathrin-mediated mechanisms as demonstrated by uptake inhibition mediated by amiloride and chlorpromazine.

  5. Theoretical studies of bonding properties and vibrational spectra of chosen ladder-like silsesquioxane clusters

    NASA Astrophysics Data System (ADS)

    Szczypka, Wojciech; Jeleń, Piotr; Koleżyński, Andrzej

    2014-10-01

    In this work the DFT calculations were carried out by means of Gaussian 09 program using B3LYP XC functional and 6-311G(d) basis set for chosen ladder-like silsesquioxane model clusters. Vibrational frequencies computations and infrared spectra were obtained subsequently for above mentioned structures. The results of topological analysis of total electron density obtained in SCF calculations (Quantum Theory of Atoms in Molecules approach) and structural analysis based on Bond Valence Method are presented in order to analyze length and ramification of ladder-like structures and various functional group influence. The calculated infrared spectra show that peak derived from vibrations of Si-O “chains” is shifting towards lower frequencies with increasing length of the ladder while at the same time, the overall strains (BVM) are diminishing.

  6. Free carbon phase in SiOC glasses derived from ladder-like silsesquioxanes

    NASA Astrophysics Data System (ADS)

    Jeleń, P.; Bik, M.; Nocuń, M.; Gawęda, M.; Długoń, E.; Sitarz, M.

    2016-12-01

    The main objective of this paper is to attempt to determine the structure of free carbon phase in SiOC glasses derived from ladder-like silsesquioxane precursors. The samples were fired in argon flowing atmosphere, in a wide temperature range (200-800° C). Conducted XRD, Raman, MIR spectroscopy research allowed to determine the structure of obtained materials. Combined XPS and Raman studies enabled to establishing the point of formation of free carbon in silicon oxycarbide matrix. Two most popular concepts were confronted with Raman and XPS results of free carbon phase in studied materials. This allowed to conclude that for temperatures below 800 °C carbon is present in a form of graphite domains inside glassy matrix.

  7. Robust superhydrophobic bridged silsesquioxane aerogels with tunable performances and their applications.

    PubMed

    Wang, Zhen; Wang, Dong; Qian, Zhenchao; Guo, Jing; Dong, Haixia; Zhao, Ning; Xu, Jian

    2015-01-28

    Aerogels are a family of highly porous materials whose applications are commonly restricted by poor mechanical properties. Herein, thiol-ene chemistry is employed to synthesize a series of novel bridged silsesquioxane (BSQ) precursors with various alkoxy groups. On the basis of the different hydrolyzing rates of the methoxy and ethoxy groups, robust superhydrophobic BSQ aerogels with tailorable morphology and mechanical performances have been prepared. The flexible thioether bridge contributes to the robustness of the as-formed aerogels, and the property can be tuned on the basis of the distinct combinations of alkoxy groups with the density of the aerogels almost unchanged. To the best of our knowledge, the lowest density among the ambient pressure dried aerogels is obtained. Further, potential application of the aerogels for oil/water separation and acoustic materials has also been presented.

  8. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    DOE PAGES

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; ...

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initialmore » monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.« less

  9. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    SciTech Connect

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.

  10. Interfacial enhancement of polypropylene composites modified with sorbitol derivatives and siloxane-silsesquioxane resin

    SciTech Connect

    Dobrzyńska-Mizera, Monika Sterzyński, Tomasz; Dutkiewicz, Michał; Di Lorenzo, Maria Laura

    2015-12-17

    Composites based on polypropylene (iPP) modified with a sorbitol derivative (NX8000) and siloxane-silsesquioxane resin (SiOPh) containing maleated polypropylene (MAPP) as compatibilizer were prepared by melt extrusion. Calorimetric investigations were carried out using differential scanning calorimetry (DSC), whereas the morphological and mechanical properties were investigated by scanning electron microscopy (SEM) and static tensile tests. DSC measurements revealed no influence of SiOPh and a slight effect of MAPP addition on the crystallization kinetics of polypropylene. Additionally, the introduction of MAPP into the iPP+NX8000+SiOPh composites increased plastic properties of the samples. All the above was attributed to the compatibilizing effect of MAPP which improved interfacial adhesion between iPP, NX8000 and SiOPh. This phenomenon was also confirmed by the SEM images illustrating more homogenous distribution of the filler in the compatibilized samples.

  11. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    PubMed Central

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-01-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V−1s−1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  12. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-04-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V‑1s‑1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements.

  13. Shape-memory polymer nanocomposites with a 3D conductive network for bidirectional actuation and locomotion application.

    PubMed

    Peng, Qingyu; Wei, Hongqiu; Qin, Yuyang; Lin, Zaishan; Zhao, Xu; Xu, Fan; Leng, Jinsong; He, Xiaodong; Cao, Anyuan; Li, Yibin

    2016-10-27

    Electrical stimulation of shape-memory polymers (SMPs) has many advantages over thermal methods; creating an efficient conductive path through the bulk polymers is essential for developing high performance electroactive systems. Here, we show that a three-dimensional (3D) porous carbon nanotube sponge can serve as a built-in integral conductive network to provide internal, homogeneous, in situ Joule heating for shape-memory polymers, thus significantly improving the mechanical and thermal behavior of SMPs. As a result, the 3D nanocomposites show a fast response and produce large exerting forces (with a maximum flexural stress of 14.6 MPa) during shape recovery. We further studied the construction of a double-layer composite structure for bidirectional actuation, in which the shape change is dominated by the temperature-dependent exerting force from the top and bottom layer, alternately. An inchworm-type robot is demonstrated whose locomotion is realized by such bidirectional shape memory. Our large stroke shape-memory nanocomposites have promising applications in many areas including artificial muscles and bionic robots.

  14. Computational exploration of polymer nanocomposite mechanical property modification via cross-linking topology.

    PubMed

    Lacevic, Naida; Gee, Richard H; Saab, Andrew; Maxwell, Robert

    2008-09-28

    Molecular dynamics simulations have been performed in order to study the effects of nanoscale filler cross-linking topologies and loading levels on the mechanical properties of a model elastomeric nanocomposite. The model system considered here is constructed from octafunctional polyhedral oligomeric silsesquioxane (POSS) dispersed in a poly(dimethylsiloxane) (PDMS) matrix. Shear moduli, G, have been computed for pure and for filled and unfilled PDMS as a function of cross-linking density, POSS fill loading level, and polymer network topology. The results reported here show that G increases as the cross-linking (covalent bonds formed between the POSS and the PDMS network) density increases. Further, G is found to have a strong dependence on cross-linking topology. The increase in shear modulus, G, for POSS filled PDMS is significantly higher than that for unfilled PDMS cross-linked with standard molecular species, suggesting an enhanced reinforcement mechanism for POSS. In contrast, in blended systems (POSS/PDMS mixture with no cross-linking) G was not observed to significantly increase with POSS loading. Finally, we find intriguing differences in the structural arrangement of bond strains between the cross-linked and the blended systems. In the unfilled PDMS the distribution of highly strained bonds appears to be random, while in the POSS filled system, the strained bonds form a netlike distribution that spans the network. Such a distribution may form a structural network "holding" the composite together and resulting in increases in G compared to an unfilled, cross-linked system. These results are of importance for engineering of new POSS-based multifunctional materials with tailor-made mechanical properties.

  15. Computational exploration of polymer nanocomposite mechanical property modification via cross-linking topology

    SciTech Connect

    Lacevic, N; Gee, R; Saab, A; Maxwell, R

    2008-04-24

    Molecular dynamics simulations have been performed in order to study the effects of nanoscale filler cross-linking topologies and loading levels on the mechanical properties of a model elastomeric nanocomposite. The model system considered here is constructed from octa-functional polyhedral oligomeric silsesquioxane (POSS) dispersed in a poly(dimethylsiloxane) (PDMS) matrix. Shear moduli, G, have been computed for pure and for filled and unfilled PDMS as a function of cross-linking density, POSS fill loading level, and polymer network topology. The results reported here show that G increases as the cross-linking (covalent bonds formed between the POSS and the PDMS network) density increases. Further, G is found to have a strong dependence on cross-linking topology. The increase in shear modulus, G, for POSS filled PDMS is significantly higher than that for unfilled PDMS cross-linked with standard molecular species, suggesting an enhanced reinforcement mechanism for POSS. In contrast, in blended systems (POSS/PDMS mixture with no cross-linking) G was not observed to significantly increase with POSS loading. Finally, we find intriguing differences in the structural arrangement of bond strains between the cross-linked and the blended systems. In the unfilled PDMS the distribution of highly strained bonds appears to be random, while in the POSS filled system, the strained bonds form a net-like distribution that spans the network. Such a distribution may form a structural network 'holding' the composite together and resulting in increases in G compared to an unfilled, cross-linked system. These results are of importance for engineering of new POSS-based multifunctional materials with tailor-made mechanical properties.

  16. Modeling the Coupled Chemo-Thermo-Mechanical Behavior of Amorphous Polymer Networks.

    SciTech Connect

    Zimmerman, Jonathan A.; Nguyen, Thao D.; Xiao, Rui

    2015-02-01

    Amorphous polymers exhibit a rich landscape of time-dependent behavior including viscoelasticity, structural relaxation, and viscoplasticity. These time-dependent mechanisms can be exploited to achieve shape-memory behavior, which allows the material to store a programmed deformed shape indefinitely and to recover entirely the undeformed shape in response to specific environmental stimulus. The shape-memory performance of amorphous polymers depends on the coordination of multiple physical mechanisms, and considerable opportunities exist to tailor the polymer structure and shape-memory programming procedure to achieve the desired performance. The goal of this project was to use a combination of theoretical, numerical and experimental methods to investigate the effect of shape memory programming, thermo-mechanical properties, and physical and environmental aging on the shape memory performance. Physical and environmental aging occurs during storage and through exposure to solvents, such as water, and can significantly alter the viscoelastic behavior and shape memory behavior of amorphous polymers. This project – executed primarily by Professor Thao Nguyen and Graduate Student Rui Xiao at Johns Hopkins University in support of a DOE/NNSA Presidential Early Career Award in Science and Engineering (PECASE) – developed a theoretical framework for chemothermo- mechanical behavior of amorphous polymers to model the effects of physical aging and solvent-induced environmental factors on their thermoviscoelastic behavior.

  17. Polymer Composite with Improved Thermal Conductivity by Constructing a Hierarchically Ordered Three-Dimensional Interconnected Network of BN.

    PubMed

    Hu, Jiantao; Huang, Yun; Yao, Yimin; Pan, Guiran; Sun, Jiajia; Zeng, Xiaoliang; Sun, Rong; Xu, Jian-Bin; Song, Bo; Wong, Ching-Ping

    2017-04-05

    In this work, we report a fabrication of epoxy resin/ordered three-dimensional boron nitride (3D-BN) network composites through combination of ice-templating self-assembly and infiltration methods. The polymer composites possess much higher thermal conductivity up to 4.42 W m(-1) K(-1) at relatively low loading 34 vol % than that of random distribution composites (1.81 W m(-1) K(-1) for epoxy/random 3D-BN composites, 1.16 W m(-1) K(-1) for epoxy/random BN composites) and exhibit a high glass transition temperature (178.9-229.2 °C) and dimensional stability (22.7 ppm/K). We attribute the increased thermal conductivity to the unique oriented 3D-BN thermally conducive network, in which the much higher thermal conductivity along the in-plane direction of BN microplatelets is most useful. This study paves the way for thermally conductive polymer composites used as thermal interface materials for next-generation electronic packaging and 3D integration circuits.

  18. Shape memory polymers

    DOEpatents

    Wilson, Thomas S.; Bearinger, Jane P.

    2015-06-09

    New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxyl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

  19. Encapsulation of titanium (IV) silsesquioxane into the NH{sub 4}USY zeolite: Preparation, characterization and application

    SciTech Connect

    Ribeiro do Carmo, Devaney Dias Filho, Newton Luiz; Ramos Stradiotto, Nelson

    2007-10-02

    This work describes the encapsulation of titanium (IV) silsesquioxane into the supercavities of NH{sub 4}USY ultra stabilized zeolite, after chemical treatment. The modified zeolite was characterized by Fourier transform infrared spectra, Nuclear magnetic resonance, scanning electronic microscopy, X-ray diffraction and thermogravity. This encapsulated titanium (IV) silsesquioxane can adsorb Azure A chloride after treatment with H{sub 3}PO{sub 4}, without modifier leaching problems. In an electrochemical study, the cyclic voltammograms of the graphite paste modified electrode, shows two redox couples with formal potential (E{sup 0}') -0.1 V and 0.21 V to I and II redox couples respectively (v=700mVs{sup -1}; Britton Robinson buffer (B-R) solution, pH 3) versus SCE ascribed to a monomer and dimmer of azure. This paper shows the use of ultra stabilized zeolite in the electrochemical field as host for molecules with nanometric dimensions.

  20. Fast Triggering of Shape Memory Polymers using an Embedded Carbon Nanotube Sponge Network.

    PubMed

    Zhou, Guoxiang; Zhang, Heng; Xu, Shuping; Gui, Xuchun; Wei, Hongqiu; Leng, Jinsong; Koratkar, Nikhil; Zhong, Jing

    2016-04-07

    In this work, a 3-D porous carbon nanotube sponge (CNTS) was embedded within a shape memory polymer (SMPs) matrix. We demonstrate complete infiltration and filling of the SMPs into the CNTS by capillary force without any damage to the CNTS structure. With only ~0.2 wt% carbon nanotube loading, the glass transition temperature is increased by ~20 °C, indicating strong interaction between CNTS and the SMPs matrix. Further, we find that the uniform distribution of the carbon nanotubes in the nanocomposite results in high electrical conductivity, and thus highly effective electricity triggering capability. The carbon nanotube sponge shape memory polymer (CNTS/SMPs) nanocomposite could be triggered within ~10 seconds by the application of ~10 volts. Results from finite element simulations showed good agreement with the experimental results, and indicated that for our system the interface thermal energy loss does not have a significant effect on the heating rate of the polymer matrix.

  1. The neural networks based modeling of a polybenzimidazole-based polymer electrolyte membrane fuel cell: Effect of temperature

    NASA Astrophysics Data System (ADS)

    Lobato, Justo; Cañizares, Pablo; Rodrigo, Manuel A.; Linares, José J.; Piuleac, Ciprian-George; Curteanu, Silvia

    Neural network models represent an important tool of Artificial Intelligence for fuel cell researchers in order to help them to elucidate the processes within the cells, by allowing optimization of materials, cells, stacks, and systems and support control systems. In this work three types of neural networks, that have as common characteristic the supervised learning control (Multilayer Perceptron, Generalized Feedforward Network and Jordan and Elman Network), have been designed to model the performance of a polybenzimidazole-polymer electrolyte membrane fuel cells operating upon a temperature range of 100-175 °C. The influence of temperature of two periods was studied: the temperature in the conditioning period and temperature when the fuel cell was operating. Three inputs variables: the conditioning temperature, the operating temperature and current density were taken into account in order to evaluate their influence upon the potential, the cathode resistance and the ohmic resistance. The Multilayer Perceptron model provides good predictions for different values of operating temperatures and potential and, hence, it is the best choice among the study models, recommended to investigate the influence of process variables of PEMFCs.

  2. Enhanced two-photon fluorescence imaging and therapy of cancer cells via Gold@bridged silsesquioxane nanoparticles.

    PubMed

    Croissant, Jonas; Maynadier, Marie; Mongin, Olivier; Hugues, Vincent; Blanchard-Desce, Mireille; Chaix, Arnaud; Cattoën, Xavier; Wong Chi Man, Michel; Gallud, Audrey; Gary-Bobo, Magali; Garcia, Marcel; Raehm, Laurence; Durand, Jean-Olivier

    2015-01-21

    A two-photon photosensitizer with four triethoxysilyl groups is synthesized through the click reaction. This photosensitizer allows the design of bridged silsesquioxane (BS) nanoparticles through a sol-gel process; moreover, gold core BS shells or BS nanoparticles decorated with gold nanospheres are synthesized. An enhancement of the two-photon properties is noted with gold and the nanoparticles are efficient for two-photon imaging and two-photon photodynamic therapy of cancer cells.

  3. Stress buildup under start-up shear flows in self-assembled transient networks of telechelic associating polymers.

    PubMed

    Koga, Tsuyoshi; Tanaka, Fumihiko; Kaneda, Isamu; Winnik, Françoise M

    2009-08-04

    The nonaffine transient network theory is used to study the time development of the shear and normal stresses under start-up shear flows in networks formed by self-assembled telechelic, hydrophobically modified water-soluble polymers. The initial slope, strain hardening, and overshoot of the shear stress are studied in detail in relation to the nonlinear tension-elongation curve of the elastically active chains in the network. The condition for the occurrence of strain hardening (upward deviation of the stress from the reference curve defined by the linear moduli) is found to be gamma > gammac(A), where gamma is the shear rate, gamma(c) is its critical value for strain hardening, and A is the amplitude of the nonlinear term in the tension of a chain. The critical shear rate gamma(c) is calculated as a function of A. It is approximately 6.3 (in the time unit of the reciprocal thermal dissociation rate) for a nonlinear chain with A = 10. The overshoot time t(max) when the stress reaches a maximum and the total deformation gamma(max) = gamma(t max) accumulated before the peak time are obtained in terms of the molecular parameters of the polymer chain. The maximum deformation gamma(max) turns out to depend weakly upon the shear rate gamma. The first and second normal stress differences are also studied on the basis of the exact numerical integration of the theoretical model by paying special attention to their overshoot, undershoot, and sign change as a function of the shear rate. These theoretical results are compared with recent rheological experiments of the solutions of telechelic hydrophobically modified poly(ethylene oxide)s carrying short branched alkyl chains (2-decyl-tetradecyl) at both ends.

  4. Materials for the Plastic Retina: Network Blends for Arrays of Polymer Grid Triodes

    DTIC Science & Technology

    1999-01-19

    sheet resistance uniformity and long-term stability. Additionally, we have synthesized several varieties of conducting polymer systems, including new PANI derivatives and Mends. The ultimate goal of this effort was...UNIAX under a joint BMDO/DARPA program). For the Plastic Retina, or the Thin Film Analog Image Processor (TAIP), a sheet resistance greater than

  5. Synthesis of chiral networks for polymer stabilized cholesteric texture (PSCT) displays

    SciTech Connect

    Rego, J.A.; Cahill, P.A.

    1997-03-01

    New mono- and di-functional polymerizable twist agents for formation of polymer stabilized cholesteric texture liquid crystal displays have been synthesized. Degree of crosslinking has a pronounced effect on electrooptic response of the cell and the stability of oriented states.

  6. Unveiling the molecular mechanism of self-healing in a telechelic, supramolecular polymer network

    NASA Astrophysics Data System (ADS)

    Yan, Tingzi; Schröter, Klaus; Herbst, Florian; Binder, Wolfgang H.; Thurn-Albrecht, Thomas

    2016-09-01

    Reversible polymeric networks can show self-healing properties due to their ability to reassemble after application of stress and fracture, but typically the relation between equilibrium molecular dynamics and self-healing kinetics has been difficult to disentangle. Here we present a well-characterized, self-assembled bulk network based on supramolecular assemblies, that allows a clear distinction between chain dynamics and network relaxation. Small angle x-ray scattering and rheological measurements provide evidence for a structurally well-defined, dense network of interconnected aggregates giving mechanical strength to the material. Different from a covalent network, the dynamic character of the supramolecular bonds enables macroscopic flow on a longer time scale and the establishment of an equilibrium structure. A combination of linear and nonlinear rheological measurements clearly identifies the terminal relaxation process as being responsible for the process of self-healing.

  7. Unveiling the molecular mechanism of self-healing in a telechelic, supramolecular polymer network

    PubMed Central

    Yan, Tingzi; Schröter, Klaus; Herbst, Florian; Binder, Wolfgang H.; Thurn-Albrecht, Thomas

    2016-01-01

    Reversible polymeric networks can show self-healing properties due to their ability to reassemble after application of stress and fracture, but typically the relation between equilibrium molecular dynamics and self-healing kinetics has been difficult to disentangle. Here we present a well-characterized, self-assembled bulk network based on supramolecular assemblies, that allows a clear distinction between chain dynamics and network relaxation. Small angle x-ray scattering and rheological measurements provide evidence for a structurally well-defined, dense network of interconnected aggregates giving mechanical strength to the material. Different from a covalent network, the dynamic character of the supramolecular bonds enables macroscopic flow on a longer time scale and the establishment of an equilibrium structure. A combination of linear and nonlinear rheological measurements clearly identifies the terminal relaxation process as being responsible for the process of self-healing. PMID:27581380

  8. Experimental and modelling studies of the shape memory properties of amorphous polymer network composites

    NASA Astrophysics Data System (ADS)

    Arrieta, J. S.; Diani, J.; Gilormini, P.

    2014-09-01

    Shape memory polymer composites (SMPCs) have become an important way to leverage improvements in the development of applications featuring shape memory polymers (SMPs). In this study, an amorphous SMP matrix has been filled with different types of reinforcements. An experimental set of results is presented and then compared to three-dimensional (3D) finite-element simulations. Thermomechanical shape memory cycles were performed in uniaxial tension. The fillers effect was studied in stress-free and constrained-strain recoveries. Experimental observations indicate complete shape recovery and put in evidence the increased sensitivity of constrained length stress recoveries to the heating ramp on the tested composites. The simulations reproduced a simplified periodic reinforced composite and used a model for the matrix material that has been previously tested on regular SMPs. The latter combines viscoelasticity at finite strain and time-temperature superposition. The simulations easily allow representation of the recovery properties of a reinforced SMP.

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

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  10. Fast Triggering of Shape Memory Polymers using an Embedded Carbon Nanotube Sponge Network

    PubMed Central

    Zhou, Guoxiang; Zhang, Heng; Xu, Shuping; Gui, Xuchun; Wei, Hongqiu; Leng, Jinsong; Koratkar, Nikhil; Zhong, Jing

    2016-01-01

    In this work, a 3-D porous carbon nanotube sponge (CNTS) was embedded within a shape memory polymer (SMPs) matrix. We demonstrate complete infiltration and filling of the SMPs into the CNTS by capillary force without any damage to the CNTS structure. With only ~0.2 wt% carbon nanotube loading, the glass transition temperature is increased by ~20 °C, indicating strong interaction between CNTS and the SMPs matrix. Further, we find that the uniform distribution of the carbon nanotubes in the nanocomposite results in high electrical conductivity, and thus highly effective electricity triggering capability. The carbon nanotube sponge shape memory polymer (CNTS/SMPs) nanocomposite could be triggered within ~10 seconds by the application of ~10 volts. Results from finite element simulations showed good agreement with the experimental results, and indicated that for our system the interface thermal energy loss does not have a significant effect on the heating rate of the polymer matrix. PMID:27052451

  11. Localised polymer networks in chiral nematic liquid crystals for high speed photonic switching

    NASA Astrophysics Data System (ADS)

    Tartan, Chloe C.; Salter, Patrick S.; Booth, Martin J.; Morris, Stephen M.; Elston, Steve J.

    2016-05-01

    Self-assembled periodic structures based upon chiral liquid crystalline materials have significant potential in the field of photonics ranging from fast-switching optoelectronic devices to low-threshold lasers. The flexoelectro-optic effect, which is observed in chiral nematic liquid crystals (LCs) when an electric field is applied perpendicular to the helical axis, has significant potential as it exhibits analogue switching in 10-100 μs. However, the major technological barrier that prohibits the commercial realisation of this electro-optic effect is the requirement of a uniform, in-plane alignment of the helix axis between glass substrates. Here, it is shown that periodic polymer structures engineered in the nematic phase of a chiral nematic LC device using direct laser writing can result in the spontaneous formation of the necessary uniform lying helix (ULH) state. Specifically, two-photon polymerization is used in conjunction with a spatial light modulator so as to correct for aberrations introduced by the bounding glass substrates enabling the polymer structures to be fabricated directly into the device. The ULH state appears to be stable in the absence of an externally applied electric field, and the optimum contrast between the bright and dark states is obtained using polymer structures that have periodicities of the order of the device thickness.

  12. Acid-doped polymer nanofiber framework: Three-dimensional proton conductive network for high-performance fuel cells

    NASA Astrophysics Data System (ADS)

    Tanaka, Manabu; Takeda, Yasushi; Wakiya, Takeru; Wakamoto, Yuta; Harigaya, Kaori; Ito, Tatsunori; Tarao, Takashi; Kawakami, Hiroyoshi

    2017-02-01

    High-performance polymer electrolyte membranes (PEMs) with excellent proton conductivity, gas barrier property, and membrane stability are desired for future fuel cells. Here we report the development of PEMs based on our proposed new concept ;Nanofiber Framework (NfF).; The NfF composite membranes composed of phytic acid-doped polybenzimidazole nanofibers (PBINf) and Nafion matrix show higher proton conductivity than the recast-Nafion membrane without nanofibers. A series of analyses reveal the formation of three-dimensional network nanostructures to conduct protons and water effectively through acid-condensed layers at the interface of PBINf and Nafion matrix. In addition, the NfF composite membrane achieves high gas barrier property and distinguished membrane stability. The fuel cell performance by the NfF composite membrane, which enables ultra-thin membranes with their thickness less than 5 μm, is superior to that by the recast-Nafion membrane, especially at low relative humidity. Such NfF-based high-performance PEM will be accomplished not only by the Nafion matrix used in this study but also by other polymer electrolyte matrices for future PEFCs.

  13. Thermally cured semi-interpenetrating electrolyte networks (s-IPN) for safe and aging-resistant secondary lithium polymer batteries

    NASA Astrophysics Data System (ADS)

    Nair, Jijeesh R.; Destro, Matteo; Bella, Federico; Appetecchi, Giovanni B.; Gerbaldi, Claudio

    2016-02-01

    Truly solid polymer electrolyte membranes are designed by thermally induced free radical polymerisation. The overall membrane architecture is built on a semi-interpenetrating polymer network (s-IPN) structure, where a di-methacrylate oligomer is cross-linked (in situ) in the presence of a long thermoplastic linear PEO chain and a supporting lithium salt to obtain a freestanding, flexible and non-tacky film. In the envisaged systems, the di-methacrylate functions as a soft cross-linker, thus avoiding physico-mechanical deformation of the s-IPNs at elevated temperature, without hampering the ionic conductivity. s-IPNs exhibit remarkable stability towards lithium metal and no traces of impurity are detected while testing their oxidation stability (4.7 V vs. Li/Li+) towards anodic potential. The newly elaborated system is also successfully tested at moderately high temperature in Li metal cells in which LiFePO4/C is used as the cathode active material, showing excellent indications of safe and highly durable electrolyte separator (i.e., 2000 cycles at reasonably high 1C rate).

  14. Semi-interpenetrating polymer networks composed of silk fibroin and poly(ethylene glycol) for wound dressing.

    PubMed

    Kweon, Haeyong; Yeo, Joo-hong; Lee, Kwang-gill; Lee, Hyun Chul; Na, Hee Sam; Won, Young Ho; Cho, Chong Su

    2008-09-01

    Semi-interpenetrating polymer networks (SIPNs) composed of silk fibroin (SF) and poly(ethylene glycol) (PEG) were prepared by photopolymerization of a PEG macromer in the presence of SF to improve the mechanical properties of SF sponge as wound dressing. The morphological structure of the SF/PEG SIPNs was observed to be composed of an interconnected microporous surface and a cross-sectional area. SF/PEG SIPNs showed non-cytotoxicity evaluated by a cell proliferation method using L929 fibroblasts. Wound contraction treated with SF/PEG SIPNs sponges was faster than that of Vaseline gauze as a control. Histological observation confirmed that the deposition of collagen in the dermis was organized by covering the wound area with SF/PEG SIPNs. The above results indicated that SF/PEG SIPNs could be used as wound dressing.

  15. Selective CO2 adsorption in a robust and water-stable porous coordination polymer with new network topology.

    PubMed

    Nagarkar, Sanjog S; Chaudhari, Abhijeet K; Ghosh, Sujit K

    2012-01-02

    A robust and water-stable porous coordination polymer [Cd(NDC)(0.5)(PCA)]·G(x) (1) (H(2)NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) with new network topology has been synthesized solvothermally. The framework is 3D porous material and forms a 1D channel along the c-axis, with the channel dimensions ~9.48 × 7.83 Å(2). The compound has high selectivity in uptake of CO(2) over other gases (H(2), O(2), Ar, N(2), and CH(4)). The framework is highly stable in presence of water vapor even at 60 °C. The high CO(2) selectivity over other gases and water stability makes the compound promising candidate for industrial postcombustion gas separation application.

  16. Nitroxide polymer networks formed by Michael addition: on site-cured electrode-active organic coating.

    PubMed

    Ibe, Takeshi; Frings, Rainer B; Lachowicz, Artur; Kyo, Soichi; Nishide, Hiroyuki

    2010-05-28

    Highly and homogeneously crosslinked poly(beta-ketoester) networks densely bearing robust nitroxide radicals were prepared via a click-type and stepwise Michael polyaddition. A half-battery cell composed of the thermally-cured radical network coatings displayed a rapid, reversible, and almost stoichiometric redox-activity even with a thickness of ca. 10 mum, which may be applicable as the electrode of organic-based rechargeable devices.

  17. Biologically Derived Soft Conducting Hydrogels Using Heparin-Doped Polymer Networks

    PubMed Central

    2015-01-01

    The emergence of flexible and stretchable electronic components expands the range of applications of electronic devices. Flexible devices are ideally suited for electronic biointerfaces because of mechanically permissive structures that conform to curvilinear structures found in native tissue. Most electronic materials used in these applications exhibit elastic moduli on the order of 0.1–1 MPa. However, many electronically excitable tissues exhibit elasticities in the range of 1–10 kPa, several orders of magnitude smaller than existing components used in flexible devices. This work describes the use of biologically derived heparins as scaffold materials for fabricating networks with hybrid electronic/ionic conductivity and ultracompliant mechanical properties. Photo-cross-linkable heparin–methacrylate hydrogels serve as templates to control the microstructure and doping of in situ polymerized polyaniline structures. Macroscopic heparin-doped polyaniline hydrogel dual networks exhibit impedances as low as Z = 4.17 Ω at 1 kHz and storage moduli of G′ = 900 ± 100 Pa. The conductivity of heparin/polyaniline networks depends on the oxidation state and microstructure of secondary polyaniline networks. Furthermore, heparin/polyaniline networks support the attachment, proliferation, and differentiation of murine myoblasts without any surface treatments. Taken together, these results suggest that heparin/polyaniline hydrogel networks exhibit suitable physical properties as an electronically active biointerface material that can match the mechanical properties of soft tissues composed of excitable cells. PMID:24738911

  18. Nanoscale electrical and mechanical characteristics of conductive polyaniline network in polymer composite films.

    PubMed

    Jafarzadeh, Shadi; Claesson, Per M; Sundell, Per-Erik; Pan, Jinshan; Thormann, Esben

    2014-11-12

    The presence and characteristics of a connected network of polyaniline (PANI) within a composite coating based on polyester acrylate (PEA) has been investigated. The bulk electrical conductivity of the composite was measured by impedance spectroscopy. It was found that the composite films containing PANI have an electrical conductivity level in the range of semiconductors (order of 10(-3) S cm(-1)), which suggests the presence of a connected network of the conductive phase. The nanoscopic distribution of such a network within the cured film was characterized by PeakForce tunneling atomic force microscopy (AFM). This method simultaneously provides local information about surface topography and nanomechanical properties, together with electrical conductivity arising from conductive paths connecting the metallic substrate to the surface of the coating. The data demonstrates that a PEA-rich layer exists at the composite-air interface, which hinders the conductive phase to be fully detected at the surface layer. However, by exposing the internal structure of the composites using a microtome, a much higher population of a conductive network of PANI, with higher elastic modulus than the PEA matrix, was observed and characterized. Local current-voltage (I-V) spectroscopy was utilized to investigate the conduction mechanism within the nanocomposite films, and revealed non-Ohmic characteristics of the conductive network.

  19. Low-voltage-exposure-enabled hydrogen silsesquioxane bilayer-like process for three-dimensional nanofabrication

    NASA Astrophysics Data System (ADS)

    Xiang, Quan; Chen, Yiqin; Wang, Yasi; Zheng, Mengjie; Li, Zhiqin; Peng, Wei; Zhou, Yanming; Feng, Bo; Chen, Yifang; Duan, Huigao

    2016-06-01

    We report a bilayer-like electron-beam lithographic process to obtain three-dimensional (3D) nanostructures by using only a single hydrogen silsesquioxane (HSQ) resist layer. The process utilizes the short penetration depth of low-energy (1.5 keV) electron irradiation to first obtain a partially cross-linked HSQ top layer and then uses a high-voltage electron beam (30 keV) to obtain self-aligned undercut (e.g. mushroom-shaped) and freestanding HSQ nanostructures. Based on the well-defined 3D resist patterns, 3D metallic nanostructures were directly fabricated with high fidelity by just depositing a metallic layer. As an example, Ag-coated mushroom-shaped nanostructures were fabricated, which showed lower plasmon resonance damping compared to their planar counterparts. In addition, the undercut 3D nanostructures also enable more reliable lift-off in comparison with the planar nanostructures, with which high-quality silver nanohole arrays were fabricated which show distinct and extraordinary optical transmission in the visible range.

  20. Synthesis and Self-Assembly Behaviors of Polyhedral Oligomeric Silsesquioxane Based Giant Molecular Shape Amphiphiles

    NASA Astrophysics Data System (ADS)

    Yue, Kan; Yu, Xinfei; Liu, Chang; Zhang, Wen-Bin; Cheng, Stephen

    2013-03-01

    Recently, our group has focus on the synthesis and characterization of novel giant molecular shape amphiphiles (GMSAs) based on functionalized molecular nanoparticles (MNPs), such as polyhedral oligomeric silsesquioxane (POSS), tethered with polymeric tails. A general synthetic method via the combination of sequential ?click? reactions has been developed and several model GMSAs with various tail lengths and distinct molecular topologies, which can be referred as the ?giant surfactants?, ?giant lipids?, ?giant gemini surfactants?, and ?giant bolaform surfactants? etc., have been demonstrated. Studies on their self-assembly behaviors in the bulk have revealed the formation of different ordered mesophase structures with feature sizes around 10 nanometers, which have been investigated in detail by small angle X-ray scattering (SAXS) technique and transmission electron microscopy (TEM). These findings have general implications on understanding the underlying principles of self-assembly behaviors of GMSAs, and might have potential applications in nano-patterning technology. This work is supported by NSF (DMR-0906898) and the Joint-Hope Foundation.

  1. Microfluidic assay of endothelial cell migration in 3D interpenetrating polymer semi-network HA-Collagen hydrogel.

    PubMed

    Jeong, Gi Seok; Kwon, Gu Han; Kang, Ah Ran; Jung, Bo Young; Park, Yongdoo; Chung, Seok; Lee, Sang-Hoon

    2011-08-01

    Cell migration through the extracellular matrix (ECM) is one of the key features for physiological and pathological processes such as angiogenesis, cancer metastasis, and wound healing. In particular, the quantitative assay of endothelial cell migration under the well-defined three dimensional (3D) microenvironment is important to analyze the angiogenesis mechanism. In this study, we report a microfluidic assay of endothelial cell sprouting and migration into an interpenetrating polymer semi-network HA-Collagen (SIPNs CH) hydrogel as ECM providing an enhanced in vivo mimicking 3D microenvironment to cells. The microfluidic chip could provide a well-controlled gradient of growth factor to cells, whereas the hydrogel could mimic a well-defined 3D microenvironment in vivo. (In addition/Furthermore, the microfluidic chip gives a well-controlled gradient of growth factor to cells) For this reason, three types of hydrogel, composed of semi-interpenetrating networks of collagen and hyaluronic acid were prepared, and firstly we proved the role of the hydrogel in endothelial cell migration. The diffusion property and swelling ratio of the hydrogel were characterized. It modulated the migration of endothelial cells in quantified manner, also being influenced by additional synthesis of Matrix metalloproteinase(MMP)-sensitive remodeling peptides and Arginine-glycine-lycinee (RGD) cell adhesion peptides. We successfully established a novel cell migration platform by changing major determinants such as ECM material under biochemical synthesis and under growth factor gradients in a microfluidic manner.

  2. Surface-Directed Assembly of Sequence-Defined Synthetic Polymers into Networks of Hexagonally Patterned Nanoribbons with Controlled Functionalities.

    PubMed

    Chen, Chun-Long; Zuckermann, Ronald N; DeYoreo, James J

    2016-05-24

    The exquisite self-assembly of proteins and peptides in nature into highly ordered functional materials has inspired innovative approaches to the design and synthesis of biomimetic materials. While sequence-defined polymers hold great promise to mimic proteins and peptides for functions, controlled assembly of them on surfaces still remains underdeveloped. Here, we report the assembly of 12-mer peptoids containing alternating acidic and aromatic monomers into networks of hexagonally patterned nanoribbons on mica surfaces. Ca(2+)-carboxylate coordination creates peptoid-peptoid and peptoid-mica interactions that control self-assembly. In situ atomic force microscopy (AFM) shows that peptoids first assemble into discrete nanoparticles; these particles then transform into hexagonally patterned nanoribbons on mica surfaces. AFM-based dynamic force spectroscopy studies show that peptoid-mica interactions are much stronger than peptoid-peptoid interactions, illuminating the driving forces for mica-directed peptoid assembly. We further demonstrate the display of functional domains at the N-terminus of assembling peptoids to produce extended networks with similar hierarchical structures. This research demonstrates that surface-directed peptoid assembly can be used as a robust platform to develop biomimetic coating materials for applications.

  3. Unusual, promoted release of guests from amphiphilic cross-linked polymer networks.

    PubMed

    Brown, Gerald O; Bergquist, Catherine; Ferm, Paul; Wooley, Karen L

    2005-08-17

    Hyperbranched fluoropolymer-poly(ethylene glycol) (HBFP-PEG) cross-linked networks have been found to exhibit capabilities for the encapsulation of high levels of geraniol guest molecules coupled with unusually rapid release of the volatile compound. The promotion of the release of the volatile fragrance geraniol, observed as decreasing volatilization temperatures and increasing volatilization rates by thermogravimetric analyses, was found to be dependent upon the HBFP-PEG network composition, with increasing effects from decreasing wt % PEG and a maximum effect occurring at 5 wt % PEG.

  4. A model of cell wall expansion based on thermodynamics of polymer networks

    NASA Technical Reports Server (NTRS)

    Veytsman, B. A.; Cosgrove, D. J.

    1998-01-01

    A theory of cell wall extension is proposed. It is shown that macroscopic properties of cell walls can be explained through the microscopic properties of interpenetrating networks of cellulose and hemicellulose. The qualitative conclusions of the theory agree with the existing experimental data. The dependence of the cell wall yield threshold on the secretion of the wall components is discussed.

  5. Effects of polymer coating on the adsorption of gas molecules on carbon nanotube networks

    SciTech Connect

    Kim, Sanghun; Lee, Hyeong Rag; Yun, Yong Ju; Ji, Seungmuk; Yoo, Kwonjae; Yun, Wan Soo; Koo, Ja-Yong; Ha, Dong Han

    2007-08-27

    Functionalization of carbon nanotubes (CNTs) with polymers such as polyethyleneimine or nafion was found to not change the adsorption properties of gas molecules on CNTs, although functionalization can remarkably enhance the sensitivity of gas sensors. Charge transfer between adsorbed molecules and single-walled carbon nanotubes (SWCNTs) at defect sites causes a steep and nonlinear conductance change at low gas concentrations, while molecules physically adsorbed on the pristine surfaces result in the linear electrical responses at higher concentrations. In addition, the molecular binding energies at defect sites of SWCNTs were measured to be 0.61 eV for NO{sub 2} and 0.53 eV for NH{sub 3}.

  6. A novel structure and photochromism of heteropolyoxometalates dispersed in polymer networks

    SciTech Connect

    Bao Xinjian; Feng Wei; Chen Jie; Liu Xiaoyang

    2012-07-15

    Nanocomposites based on Keggin structure tungstophosphate acid (PWA) with 'branch-like' nanometer well dispersed in poly(acrylamide-co-vinylamine) (PAM-co-PVAm) were fabricated. The microstructure and photochromic properties were studied via Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM), ultraviolet-visible spectra (UV-vis) and electron resonance spectra (ESR). FT-IR results showed that the Keggin geometry of polyoxometalates was still preserved inside the composites and hydrogen bonding and salt formation were built between PWA and polymer matrix. SEM and TEM images showed that PWA nanoparticles were finely dispersed in polymer matrix with 'branch-like' shape. Under UV irradiation, the film was reduced photochemically to yield a glaucous species. After UV light turned off, the color of film became green. Two photo-reduction processes (one was between acylamino and heteropoly acid, another was between amidocyanogen and heteropoly acid) occurred at the same time in PWA/PAM-co-PVAm system, which resulted in the formation of heteropolygreen. - Graphical abstract: Two absorption bands appeared after UV irradiated. In bleaching process, the peaks at 620-820 nm disappeared and those at 420 nm still presented. Due to synergies happened between heteropolyacid and PAM-co-PVAm, heteropolygreen was formed. Highlights: Black-Right-Pointing-Pointer 'Branch-like' composites were fabricated by dispersed PWA into PAM-co-PVAm system. Black-Right-Pointing-Pointer Two photo-reduction processes occurred simultaneously in PWA/PAM-co-PVAm system. Black-Right-Pointing-Pointer Heteropolygreen was formed by synergies of hydrogen bonding and salt formation.

  7. Perfluorinated polymer electrolytes hybridized with in situ grown titania quasi-networks.

    PubMed

    Patil, Yatin; Sambandam, Satheesh; Ramani, Vijay; Mauritz, Kenneth

    2013-01-01

    Perfluorinated Nafion membranes, neutralized to various extents, were hybridized with titania quasi-networks that were grown in situ via catalyzed sol-gel reactions of an titanium isopropoxide precursor. The formation of Ti-O-Ti groups within the ionomer was verified by FTIR-ATR spectroscopy. EDAX studies confirmed that the extent of propagation of titania quasi-networks into the bulk of the ionomer film increased with ionomer neutralization. Compared to the unmodified control membrane, the hybrid membranes exhibited superior dimensional stability, modulus, stress, and strain at break and gas barrier properties. All hybrid membranes exhibited superior resistance to degradation when subjected to an accelerated stress test in an operating fuel cell environment, as a resultant of the better dimensional stability and gas barrier properties induced through addition of the inorganic titania phase.

  8. Effective conductivity of particulate polymer composite electrolytes using random resistor network method

    SciTech Connect

    Kalnaus, Sergiy; Sabau, Adrian S; Newman, Sarah M; Tenhaeff, Wyatt E; Daniel, Claus; Dudney, Nancy J

    2011-01-01

    The effective DC conductivity of particulate composite electrolytes was obtained by solving electrostatics equations using random resistors network method in three dimensions. The composite structure was considered to consist of three phases: matrix, particulate filler, and conductive shell that surrounded each particle; each phase possessing a different conductivity. Different particle size distributions were generated using Monte Carlo simulations. Unlike effective medium formulations, it was shown that the random resistors network method was able to predict percolation thresholds for the effective composite conductivity. It was found that the mean particle radius has a higher influence on the effective composite conductivity compared to the effect of type of the particle size distributions that were considered. The effect of the shell thickness on the composite conductivity has been investigated. It was found that the conductivity enhancement due to the presence of the conductive shell phase becomes less evident as the shell thickness increases.

  9. Using mesoscopic models to design strong and tough biomimetic polymer networks.

    PubMed

    Salib, Isaac G; Kolmakov, German V; Bucior, Benjamin J; Peleg, Orit; Kröger, Martin; Savin, Thierry; Vogel, Viola; Matyjaszewski, Krzysztof; Balazs, Anna C

    2011-11-15

    Using computational modeling, we investigate the mechanical properties of polymeric materials composed of coiled chains, or "globules", which encompass a folded secondary structure and are cross-linked by labile bonds to form a macroscopic network. In the presence of an applied force, the globules can unfold into linear chains and thereby dissipate energy as the network is deformed; the latter attribute can contribute to the toughness of the material. Our goal is to determine how to tailor the labile intra- and intermolecular bonds within the network to produce material exhibiting both toughness and strength. Herein, we use the lattice spring model (LSM) to simulate the globules and the cross-linked network. We also utilize our modified Hierarchical Bell model (MHBM) to simulate the rupture and reforming of N parallel bonds. By applying a tensile deformation, we demonstrate that the mechanical properties of the system are sensitive to the values of N(in) and N(out), the respective values of N for the intra- and intermolecular bonds. We find that the strength of the material is mainly controlled by the value of N(out), with the higher value of N(out) providing a stronger material. We also find that, if N(in) is smaller than N(out), the globules can unfold under the tensile load before the sample fractures and, in this manner, can increase the ductility of the sample. Our results provide effective strategies for exploiting relatively weak, labile interactions (e.g., hydrogen bonding or the thiol/disulfide exchange reaction) in both the intra- and intermolecular bonds to tailor the macroscopic performance of the materials.

  10. Physicochemical characterisation and biological evaluation of hydrogel-poly(epsilon-caprolactone) interpenetrating polymer networks as novel urinary biomaterials.

    PubMed

    Jones, David S; McLaughlin, David W J; McCoy, Colin P; Gorman, Sean P

    2005-05-01

    Hydrogels are frequently employed as medical device biomaterials due to their advantageous biological properties, e.g. resistance to infection and encrustation, biocompatibility; however, their poor mechanical properties generally limit the scope of application to coatings of medical devices. To address this limitation, this study described the formulation of sequential interpenetrating polymer networks (IPN) of poly(-caprolactone) (PCL) and poly(hydroxyethylmethacrylate) (p(HEMA)). IPN containing 20% w/w PCL, p(HEMA), both in the presence or absence of ethyleneglycol dimethacrylate (EGDMA 1% w/w), were prepared by free radical polymerisation. Following preparation the degradation and the mechanical and surface properties of the biomaterials and, in addition, the resistances to microbial adherence and encrustation in vitro were examined. In comparison to p(HEMA) the various IPN exhibited substantially greater tensile properties (ultimate tensile strength, % elongation, Young's modulus) that were accredited to the discrete distribution of PCL within the hydrogel network. The IPN exhibited two glass transition temperatures that were statistically similar to those of the individual components, thereby providing evidence of the immiscible nature of the two polymers. The IPN possessed higher receding contact angles and lower equilibrium water contents in comparison to p(HEMA), whereas the limited degradation of the IPN at both pH 7 and 9 was deemed suitable for clinical usage for periods of at least 4 weeks. The resistances of the various IPN to bacterial adherence and urinary encrustation were examined using in vitro models. Importantly the resistance of the IPN to encrustation was, in general, similar to that of p(HEMA) but greater than that of PCL whereas, the resistance of the IPN to bacterial adherence was frequently greater than that of p(HEMA) and PCL. Therefore, this study has shown that the mechanical properties of p(HEMA) may be substantially increased by the

  11. Ion Transport Mechanism of a Gel Electrolyte Comprising a Salt in Binary Plastic Crystalline Mixtures Confined inside a Polymer Network.

    PubMed

    Sen, Sudeshna; Malunavar, Sneha; Bhattacharyya, Aninda J

    2016-09-21

    We discuss here the ion transport mechanism of a gel electrolyte comprising lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solvated by two plastic crystalline solvents, one a solid (succinonitrile, abbreviated as SN) and another (a room temperature ionic liquid) (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, (abbreviated as IL) confined inside a linear network of poly(methyl methacrylate) (PMMA). The concentration of the IL component (x) determines the physical properties of the unconfined electrolyte (i.e., SN1-xILx-LiTFSI) and when confined inside the polymer network (GPE-x). The extent of disorder in the SN1-xILx-LiTFSI and the GPE-x electrolytes is enhanced compared to both the bare SN-LiTFSI and IL-LiTFSI electrolytes. The enhanced disordering in the plastic phase alters both the local ion environment and viscosity. These changes strongly influence the ion mobility and nature of predominant charge carriers and thus the ion conduction mechanism in SN1-xILx-LiTFSI and GPE-x. The proposed SN1-xILx-LiTFSI and the GPE-x electrolytes show predominantly anion conduction (tTFSI ≈ 0.5); however, lithium transference number (tLi ≈ 0.2) is nearly an order higher than the IL-LiTFSI (tLi ≈ 0.02-0.06). The ionic conductivity of SN1-xILx-LiTFSI is much higher (especially for x ≈ 0.1) compared to both SN-LiTFSI and IL-LiTFSI. The ionic conductivity of the GPE-x, though lower than the unconfined SN1-xILx-LiTFSI electrolytes, is still very promising, displaying values of ∼10(-3) Ω(-1) cm(-1). The GPE-x displayed compliable mechanical properties, stable Li-electrode/electrolyte interface, low rate of Al corrosion, and stable cyclability over several tens of charge-discharge cycles when assembled in a separator-free Li-graphite cell. The promising electrochemical performance further justifies the simple strategy of employing mixed physical state plasticizers to tune the physical properties of polymer electrolytes requisite for application in

  12. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    SciTech Connect

    Gu, Jin-Zhong; Wu, Jiang; Kirillov, Alexander M.; Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai

    2014-05-01

    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  13. Electrophoretic mobility of semi-flexible double-stranded DNA in defect-controlled polymer networks: Mechanism investigation and role of structural parameters.

    PubMed

    Khairulina, Kateryna; Li, Xiang; Nishi, Kengo; Shibayama, Mitsuhiro; Chung, Ung-il; Sakai, Takamasa

    2015-06-21

    Our previous studies have reported an empirical model, which explains the electrophoretic mobility (μ) of double-stranded DNA (dsDNA) as a combination of a basic migration term (Rouse-like or reptation) and entropy loss term in polymer gels with ideal network structure. However, this case is of exception, considering a large amount of heterogeneity in the conventional polymer gels. In this study, we systematically tune the heterogeneity in the polymer gels and study the migration of dsDNA in these gels. Our experimental data well agree with the model found for ideal networks. The basic migration mechanism (Rouse-like or reptation) persists perfectly in the conventional heterogeneous polymer gel system, while the entropy loss term continuously changes with increase in the heterogeneity. Furthermore, we found that in the limit where dsDNA is shorter than dsDNA persistence length, the entropy loss term may be related to the collisional motions between DNA fragments and the cross-links.

  14. Polymer stabilization of the smectic C-alpha* liquid crystal phase—Over tenfold thermal stabilization by confining networks of photo-polymerized reactive mesogens

    NASA Astrophysics Data System (ADS)

    Labeeb, A.; Gleeson, H. F.; Hegmann, T.

    2015-12-01

    The smectic C*-alpha (SmCα*) phase is one of the sub-phases of ferroelectric liquid crystals that has drawn much interest due to its electro-optical properties and ultrafast switching. Generally observed above the ferroelectric SmC* phase in temperature, the SmCα* commonly shows only very narrow phase temperature range of a few degree Celsius. To broaden the SmCα* phase, polymer stabilization was investigated for thermal phase stabilization. Two different reactive monomers were tested in three mixtures, and all three broadened the temperature range of the SmCα* phase from 3 °C to 39 °C. The current reversal method was used to determine the phase existence versus temperature. Moreover, the texture and network structure was studied by polarized optical microscopy and scanning electron microscopy, with the latter revealing the confinement of the smectic layer structure within the porous polymer network.

  15. New nanoplatforms based on UCNPs linking with polyhedral oligomeric silsesquioxane (POSS) for multimodal bioimaging

    NASA Astrophysics Data System (ADS)

    Ge, Xiaoqian; Dong, Liang; Sun, Lining; Song, Zhengmei; Wei, Ruoyan; Shi, Liyi; Chen, Haige

    2015-04-01

    A new and facile method was used to transfer upconversion luminescent nanoparticles from hydrophobic to hydrophilic using polyhedral oligomeric silsesquioxane (POSS) linking on the surface of upconversion nanoparticles. In comparison with the unmodified upconversion nanoparticles, the POSS modified upconversion nanoplatforms [POSS-UCNPs(Er), POSS-UCNPs(Tm)] displayed good monodispersion in water and exhibited good water-solubility, while their particle size did not change substantially. Due to the low cytotoxicity and good biocompatibility as determined by methyl thiazolyl tetrazolium (MTT) assay and histology and hematology analysis, the POSS modified upconversion nanoplatforms were successfully applied to upconversion luminescence imaging of living cells in vitro and nude mouse in vivo (upon excitation at 980 nm). In addition, the doped Gd3+ ion endows the POSS-UCNPs with effective T1 signal enhancement and the POSS-UCNPs were successfully applied to in vivo magnetic resonance imaging (MRI) for a Kunming mouse, which makes them potential MRI positive-contrast agents. More importantly, the corner organic groups of POSS can be easily modified, resulting in kinds of POSS-UCNPs with many potential applications. Therefore, the method and results may provide more exciting opportunities for multimodal bioimaging and multifunctional applications.A new and facile method was used to transfer upconversion luminescent nanoparticles from hydrophobic to hydrophilic using polyhedral oligomeric silsesquioxane (POSS) linking on the surface of upconversion nanoparticles. In comparison with the unmodified upconversion nanoparticles, the POSS modified upconversion nanoplatforms [POSS-UCNPs(Er), POSS-UCNPs(Tm)] displayed good monodispersion in water and exhibited good water-solubility, while their particle size did not change substantially. Due to the low cytotoxicity and good biocompatibility as determined by methyl thiazolyl tetrazolium (MTT) assay and histology and hematology

  16. Modeling transmission parameters of polymer microstructured fibers for applications in FTTH networks

    NASA Astrophysics Data System (ADS)

    Gdula, P.; Welikow, K.; Szczepański, P.; Buczyński, R.; Piramidowicz, R.

    2011-10-01

    This paper is focused on selected aspects of designing and modeling of transmission parameters of plastic optical fibers (POFs), considered in the context of their potential applications in optical access networks and, specifically, in Fiber-To- The-Home (FTTH) systems. The survey of state-of-the-art solutions is presented and possibility of improving transmission properties of POFs by microstructurization is discussed on the basis of the first results of numerical modeling. In particular, the microstructured POF was designed supporting propagation of limited number of modes while keeping relatively large mode area and, simultaneously, significantly lowered bending losses.

  17. Marginal integrity of restorations produced with a model composite based on polyhedral oligomeric silsesquioxane (POSS)

    PubMed Central

    CORREA, Luciano Ribeiro; BORGES, Alexandre Luiz Souto; GUIMARÃES, Heloisa Bailly; ALMEIDA, Elis Regina Nunes; POSKUS, Laiza Tatiana; SILVA, Eduardo Moreira

    2015-01-01

    Marginal integrity is one of the most crucial aspects involved in the clinical longevity of resin composite restorations. Objective To analyze the marginal integrity of restorations produced with a model composite based on polyhedral oligomeric silsesquioxane (POSS). Material and Methods A base composite (B) was produced with an organic matrix with UDMA/TEGDMA and 70 wt.% of barium borosilicate glass particles. To produce the model composite, 25 wt.% of UDMA were replaced by POSS (P25). The composites P90 and TPH3 (TP3) were used as positive and negative controls, respectively. Marginal integrity (%MI) was analyzed in bonded class I cavities. The volumetric polymerization shrinkage (%VS) and the polymerization shrinkage stress (Pss - MPa) were also evaluated. Results The values for %MI were as follows: P90 (100%) = TP3 (98.3%) = B (96.9%) > P25 (93.2%), (p<0.05). The %VS ranged from 1.4% (P90) to 4.9% (P25), while Pss ranged from 2.3 MPa (P90) to 3.9 MPa (B). For both properties, the composite P25 presented the worst results (4.9% and 3.6 MPa). Linear regression analysis showed a strong positive correlation between %VS and Pss (r=0.97), whereas the correlation between Pss and %MI was found to be moderate (r=0.76). Conclusions The addition of 25 wt.% of POSS in methacrylate organic matrix did not improve the marginal integrity of class I restorations. Filtek P90 showed lower polymerization shrinkage and shrinkage stress when compared to the experimental and commercial methacrylate composite. PMID:26537714

  18. Organic-inorganic hybrid compounds containing polyhedral oligomeric silsesquioxane for conservation of stone heritage.

    PubMed

    Son, Seunghwan; Won, Jongok; Kim, Jeong-Jin; Jang, Yun Deuk; Kang, Yong Soo; Kim, Sa Dug

    2009-02-01

    Alkoxysilane solutions based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying heritage stone surfaces. TEOS-based products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the grains of stone components. However, they suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developing capillary force and dense gel fractures left inside of the stone. In this study, a TEOS-based stone consolidant containing functional (3-glycidoxypropyl)trimethoxysilane (GPTMS) and polyhedral oligomeric silsesquioxane (POSS) has been prepared in order to reduce gel crack formation during the drying phase. The addition of nanometer-sized POSS and/or GPTMS having a flexible segment reduces the capillary force developed during solvent evaporation. The properties of the TEOS/GPTMS/POSS composite solutions were compared with those of commercial products (Wacker OH and Unil sandsteinfestiger OH 1:1). The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/POSS solution was stable over a period of up to 6 months. The addition of POSS and GPTMS provided a crack-free gel, while the gel from the commercial consolidants exhibited cracks after drying. The surface hydrophobicity of the treated decayed granite increased with the addition of POSS and GPTMS, and it was higher than that of the commercial product, implying the possibility of POSS and GPTMS as barriers to the penetration of water. This result implies that the TEOS/GPTMS/POSS solution showed a high suitability for the consolidation of granite heritage.

  19. Fabrication of two-dimensional visible wavelength nanoscale plasmonic structures using hydrogen silsesquioxane based resist

    NASA Astrophysics Data System (ADS)

    Smith, Kyle Z.; Gadde, Akshitha; Kadiyala, Anand; Dawson, Jeremy M.

    2016-03-01

    In recent years, the global market for biosensors has continued to increase in combination with their expanding use in areas such as biodefense/detection, home diagnostics, biometric identification, etc. A constant necessity for inexpensive, portable bio-sensing methods, while still remaining simple to understand and operate, is the motivation behind novel concepts and designs. Labeled visible spectrum bio-sensing systems provide instant feedback that is both simple and easy to work with, but are limited by the light intensity thresholds required by the imaging systems. In comparison, label-free bio-sensing systems and other detection modalities like electrochemical, frequency resonance, thermal change, etc., can require additional technical processing steps to convey the final result, increasing the system's complexity and possibly the time required for analysis. Further decrease in the detection limit can be achieved through the addition of plasmonic structures into labeled bio-sensing systems. Nano-structures that operate in the visible spectrum have feature sizes typically in the order of the operating wavelength, calling for high aspect ratio nanoscale fabrication capabilities. In order to achieve these dimensions, electron beam lithography (EBL) is used due to its accurate feature production. Hydrogen silsesquioxane (HSQ) based electron beam resist is chosen for one of its benefits, which is after exposure to oxygen plasma, the patterned resist cures into silicon dioxide (SiO2). These cured features in conjunction with nanoscale gold particles help in producing a high electric field through dipole generation. In this work, a detailed process flow of the fabrication of square lattice of plasmonic structures comprising of gold coated silicon dioxide pillars designed to operate at 560 nm wavelength and produce an intensity increase of roughly 100 percent will be presented.

  20. Curvature-induced crosshatched order in two-dimensional semiflexible polymer networks

    NASA Astrophysics Data System (ADS)

    Vrusch, Cyril; Storm, Cornelis

    2015-12-01

    A recurring motif in the organization of biological tissues are networks of long, fibrillar protein strands effectively confined to cylindrical surfaces. Often, the fibers in such curved, quasi-two-dimensional (2D) geometries adopt a characteristic order: the fibers wrap around the central axis at an angle which varies with radius and, in several cases, is strongly bimodally distributed. In this Rapid Communication, we investigate the general problem of a 2D crosslinked network of semiflexible fibers confined to a cylindrical substrate, and demonstrate that in such systems the trade-off between bending and stretching energies, very generically, gives rise to crosshatched order. We discuss its general dependency on the radius of the confining cylinder, and present an intuitive model that illustrates the basic physical principle of curvature-induced order. Our findings shed new light on the potential origin of some curiously universal fiber orientational distributions in tissue biology, and suggests novel ways in which synthetic polymeric soft materials may be instructed or programmed to exhibit preselected macromolecular ordering.

  1. Transient Binding and Viscous Dissipation in Semi-flexible Polymer Networks

    NASA Astrophysics Data System (ADS)

    Lieleg, Oliver; Claessens, Mireille; Bausch, Andreas

    2008-03-01

    Nature specifically chooses from a myriad of actin binding proteins (ABPs) to tailor the cytoskeletal microstructure. Herein, cells rely on the dynamics of the cytoskeleton as its structural and mechanical adaptability is crucial to allow for dynamic processes. A molecular understanding of such biological complexity calls for an in vitro system with well-defined structural rearrangements and cross-linker dynamics to elucidate the physical origin of the unique viscoelastic properties of cells. As we present here, the frequency-dependent viscoelastic response of cross-linked in vitro actin networks is determined by the binding kinetics of cross-linking molecules. Independent from the particular network structure, the viscous dissipation (loss modulus) exhibits a pronounced minimum in an intermediate frequency which is dominated by elasticity. We show that in this frequency regime the molecular origin of the viscoelastic response is given by the non-static nature of actin/ABP bonds as they are subjugated to chemical on/off kinetics. The time scale of the resulting stress release is set by the lifetime distribution of the cross-linking molecule and therefore can be tuned independently from other relaxation mechanisms. We speculate that unbinding of distinct cross-links might be the molecular mechanism employed by cells for mechanosensing.

  2. Development of Hierarchical Polymer@Pd Nanowire-Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink.

    PubMed

    Mir, Sajjad Husain; Ochiai, Bungo

    2016-06-01

    A facile one-pot approach for preparing hierarchical nanowire-networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal-complexation-induced phase separation with functionalized graft copolymers and subsequent self-assembly of PdNPs. The nanospheres hierarchically assembled into the nanowire-network upon drying. The Pd nanowire-network served as an active catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling reactions. As low as 500 μmol % Pd was sufficient for quantitative reactions, and the origin of the high activity is ascribed to the highly active sites originating from high-index facets, kinks, and coalesced structures. The catalyst can be recycled via simple filtration and washing, maintaining its high activity owing to the micrometer-sized hierarchical structure of the nanomaterial. The polymer@Pd nanosphere also served as a printable conductive ink for a translucent grid pattern with excellent horizontal conductivity (7.5×10(5) S m(-1)).

  3. Development of Hierarchical Polymer@Pd Nanowire‐Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink

    PubMed Central

    Mir, Sajjad Husain

    2016-01-01

    Abstract A facile one‐pot approach for preparing hierarchical nanowire‐networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal‐complexation‐induced phase separation with functionalized graft copolymers and subsequent self‐assembly of PdNPs. The nanospheres hierarchically assembled into the nanowire‐network upon drying. The Pd nanowire‐network served as an active catalyst for Mizoroki–Heck and Suzuki–Miyaura coupling reactions. As low as 500 μmol % Pd was sufficient for quantitative reactions, and the origin of the high activity is ascribed to the highly active sites originating from high‐index facets, kinks, and coalesced structures. The catalyst can be recycled via simple filtration and washing, maintaining its high activity owing to the micrometer‐sized hierarchical structure of the nanomaterial. The polymer@Pd nanosphere also served as a printable conductive ink for a translucent grid pattern with excellent horizontal conductivity (7.5×105 S m−1). PMID:27551657

  4. Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

    PubMed Central

    Kim, Ju-Myung; Park, Jang-Hoon; Lee, Chang Kee; Lee, Sang-Young

    2014-01-01

    As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries. PMID:24710575

  5. In Vivo Evaluation of a PEO-Gellan Gum Semi-Interpenetrating Polymer Network for the Oral Delivery of Sulpiride.

    PubMed

    Hoosain, Famida G; Choonara, Yahya E; Kumar, Pradeep; Tomar, Lomas K; Tyagi, Charu; du Toit, Lisa C; Pillay, Viness

    2016-05-16

    In this study, an optimized epichlorohydrin-crosslinked semi-interpenetrating polymer network xerogel matrix system (XePoMas) for the controlled delivery of sulpiride was prepared. The ability of XePoMas to sustain drug release was determined by in vitro and in vivo drug release experiments. Swelling of the xerogel over the 24-h experimental period ranged from 346 to 648%; swelling was observed to increase exponentially over the initial 8 h. In vitro drug release depicted a linear zero order drug release profile with an R (2) value of 0.9956. The ability of the fabricated XePoMas to sustain drug release and enhance bioavailability of sulpiride in vivo was investigated by evaluating the plasma drug concentration over 24 h in the large pig model. The optimized XePoMas formulation was shown to increase intestinal absorption of sulpiride to a greater extent than the marketed product in vivo, with a C max of 830.58 ng/mL after 15 h.

  6. Characterization of submillisecond response optical addressing phase modulator based on low light scattering polymer network liquid crystal

    SciTech Connect

    Xiangjie, Zhao E-mail: zxjdouble@gmail.com; Cangli, Liu; Jiazhu, Duan; Dayong, Zhang; Yongquan, Luo

    2015-01-07

    Optically addressed conventional nematic liquid crystal spatial light modulator has attracted wide research interests. But the slow response speed limited its further application. In this paper, polymer network liquid crystal (PNLC) was proposed to replace the conventional nematic liquid crystal to enhance the response time to the order of submillisecond. The maximum light scattering of the employed PNLC was suppressed to be less than 2% at 1.064 μm by optimizing polymerization conditions and selecting large viscosity liquid crystal as solvent. The occurrence of phase ripple phenomenon due to electron diffusion and drift in photoconductor was found to deteriorate the phase modulation effect of the optical addressed PNLC phase modulator. The wavelength effect and AC voltage frequency effect on the on state dynamic response of phase change was investigated by experimental methods. These effects were interpreted by electron diffusion and drift theory based on the assumption that free electron was inhomogeneously distributed in accordance with the writing beam intensity distribution along the incident direction. The experimental results indicated that the phase ripple could be suppressed by optimizing the wavelength of the writing beam and the driving AC voltage frequency when varying the writing beam intensity to generate phase change in 2π range. The modulation transfer function was also measured.

  7. Simulation and theory of self-assembly and network formation in reversibly cross-linked equilibrium polymers

    NASA Astrophysics Data System (ADS)

    Kindt, James T.

    2005-10-01

    A simulation model of hard spheres capable of reversible assembly into chains, which then may reversibly cross-link into networks, has been studied through grand canonical Monte Carlo simulation. Effects of varying intra- and interchain bond strengths, chain flexibilities, and restrictions on cross-linking angle were investigated. Observations including chain-length distributions and phase separation could be captured in most cases using a simple model theory. The coupling of chain growth to cross-linking was shown to be highly sensitive to the treatment of cross-linking by chain ends. In some systems, ladderlike domains of several cross-links joining two chains were common, resulting from cooperativity in the cross-linking. Extended to account for this phenomenon, the model theory predicts that such cooperativity will suppress phase separation in weakly polymerizing chains and at high cross-link concentration. In the present model, cross-linking stabilizes the isotropic phase with respect to the nematic phase, causing a shift in the isotropic-nematic transition to higher monomer concentration than in simple equilibrium polymers.

  8. Covalent organic/inorganic hybrid proton-conductive membrane with semi-interpenetrating polymer network: Preparation and characterizations

    NASA Astrophysics Data System (ADS)

    Fu, Rong-Qiang; Woo, Jung-Je; Seo, Seok-Jun; Lee, Jae-Suk; Moon, Seung-Hyeon

    2008-05-01

    A series of new covalent organic/inorganic hybrid proton-conductive membranes, each with a semi-interpenetrating polymer network (semi-IPN), for direct methanol fuel cell (DMFC) applications is prepared through the following sequence: (i) copolymerization of impregnated styrene (St), p-vinylbenzyl chloride (VBC) and divinylbenzene (DVB) within a supporting polyvinyl chloride (PVC) film; (ii) reaction of the chloromethyl group with 3-(methylamine)propyl-trimethoxysilane (MAPTMS); (ii) a sol-gel process under acidic conditions; (iv) a sulfonation reaction. The developed membranes are characterized in terms of Fourier transform infrared/attenuated total reflectance (FTIR/ATR), scanning electron microscopy/energy-dispersive X-ray analysis (SEM/EDXA), elemental analysis (EA) and thermogravimetric analysis (TGA), which confirm the formation of the target membranes. The developed copolymer chains are interpenetrating with the PVC matrix to form the semi-IPN structure, and the inorganic silica is covalently bound to the copolymers. These features provide the membranes with high mechanical strength. The effect of silica content is investigated. As the silica content increases, proton conductivity and water content decrease, whereas oxidative stability is improved. In particular, methanol permeability and methanol uptake are reduced largely by the silica. The ratio of proton conductivity to methanol permeability for the hybrid membranes is higher than that of Nafion 117. All these properties make the hybrid membranes a potential candidate for DMFC applications.

  9. Enhanced ultraviolet photocatalytic activity of Ag/ZnO nanoparticles synthesized by modified polymer-network gel method

    NASA Astrophysics Data System (ADS)

    Lu, Y. H.; Xu, M.; Xu, L. X.; Zhang, C. L.; Zhang, Q. P.; Xu, X. N.; Xu, S.; Ostrikov, K.

    2015-09-01

    Ag/ZnO nanoparticle (NP) heterostructures are synthesized through a modified polymer-network gel method in which glucose is added to the precursor solution to prevent the gel from drastically shrinking during drying of the aqueous solution. Structural and optical properties of the samples are characterized by a range of techniques including XRD, SEM, TEM, XPS, UV-Vis, and PL. The high-quality Ag-ZnO heterostructure is evidenced clearly by high-resolution TEM. The Ag/ZnO heterostructure nanocomposites exhibit a higher photocatalytic activity in the degradation of methyl orange than pure ZnO. Especially, Ag/ZnO NP heterostructures with the Ag/Zn molar ratio of 5:95 (sample ZA-5) show the highest degradation efficiency, which is 11 times higher compared with pure ZnO. The photoluminescence properties of the heterostructures and O defect states are studied to well explain the observed photocatalytic effects. ZA-5 also exhibits competitive photocatalytic activity for the degradation of other pollutant dyes such as Methylene blue and Rhodamine B compared with the recently reported techniques, while showing excellent catalyst photostability as well as offering simplicity and reliability.

  10. Drug release from interpenetrating polymer networks based on poly(ethylene glycol) methyl ether acrylate and gelatin.

    PubMed

    Ding, Frank; Hsu, S-H; Wu, D-H; Chiang, W-Y

    2009-01-01

    In order to develop new materials for biomedical and pharmaceutical applications, interpenetrating polymer networks (IPNs) based on poly(ethylene glycol) methyl ether acrylate (PEGMEA) and gelatin were synthesized. These two materials were cross-linked sequentially using N,N'-methylene bisacrylamide (NMBA) and glutaraldehyde (Glu). Two series of IPNs gels were synthesized by applying different amounts of PEGMEA and gelatin in the initial feed. Sequential IPNs were prepared by polymerizing and cross-linking PEGMEA in the presence of gelatin using redox initiators (e.g., ammonium peroxydisulfate (APS) and N,N,N',N'-tetramethyl ethylenediamine (TEMED)), as well as NMBA as the cross-linking agent. Gelatin in firm gel was then cross-linked with 1% glutaraldehyde. The swelling kinetics, mechanical properties and drug-release behavior of these IPNs were analyzed. The surface properties were examined by scanning electron microscopy. The results indicated that the swelling ratio decreased with an increase in the content of both PEGMEA and gelatin in the IPNs. PEGMEA/gelatin-based full-IPNs had a significantly higher shear modulus (G) and cross-linking density (rho) when the content of PEGMEA was increased. The drug loading was very high due to the full-IPN structure. The drug-release velocity was mainly affected by the content of PEGMEA.

  11. Mechanoluminescent Imaging of Osmotic Stress-Induced Damage in a Glassy Polymer Network

    PubMed Central

    2017-01-01

    A chemiluminescent mechanophore, bis(adamantyl-1,2-dioxetane), is used to investigate the covalent bond scission resulting from the sorption of chloroform by glassy poly(methyl methacrylate) (PMMA) networks. Bis(adamantyl)-1,2-dioxetane units incorporated as cross-linkers underwent mechanoluminescent scission, demonstrating that solvent ingress caused covalent bond scission. At higher cross-linking densities, the light emission took the form of hundreds of discrete bursts, widely varying in intensity, with each burst composed of 107–109 photons. Camera imaging indicated a relatively slow propagation of bursts through the material and permitted analysis of the spatial correlation between the discrete bond-breaking events. The implications of these observations for the mechanism of sorption and fracture are discussed. PMID:28316344

  12. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    NASA Astrophysics Data System (ADS)

    Gu, Jin-Zhong; Wu, Jiang; Kirillov, Alexander M.; Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai

    2014-05-01

    A series of six coordination compounds {[Zn(5-Brnic)2]·1.5H2O}n (1), [Cd(5-Brnic)2]n (2), [Co(5-Brnic)2(H2O)2]n (3), [Zn(5-Brnic)2(H2biim)]n (4), {[Cd(5-Brnic)2(phen)]·H2O}n (5), and [Pb(5-Brnic)2(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2‧-biimidazole (H2biim) ligand. All the products 1-6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N-H⋯O and C-H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail.

  13. Polyhedral Oligomeric Silsesquioxane-Functionalized Perfluorocyclobutyl Aryl Ether Polymers: An Overview of the Synthesis and Properties of Polyhedral Oligomeric Silsesquioxanes (POSS) Functionalized with Perfluorocyclobutyl (PFCB) Aryl Ether Polymer Blends and Copolymers (Preprint)

    DTIC Science & Technology

    2007-10-17

    Contact Analyzer System or a Rime-Hart 100-00 115 Goniometry. Liquid drops were either automatically or manually dispensed with 8 10 L drop sizes...C.; Barthlott, W. Ann. Bot. 1997, 79, 677. 2. Barthlott, W.; Nenhuis, C. Planta 1997, 202, 1. 3. Sun, T.; Feng, L.; Gao, X.; Jian, L. Acc

  14. Photo-Reactive Nanogel as a Means to Tune Properties during Polymer Network Formation

    PubMed Central

    Liu, JianCheng; Rad, Ima Y.; Sun, Fang; Stansbury, Jeffrey W.

    2013-01-01

    Photo-reactive nanogels with an integrated photoinitiator-based functionality were synthesized via a Reversible Addition-Fragmentation Chain Transfer (RAFT) process. Without additional free initiators, this nanogel is capable of radical generation and initiating polymerization of a secondary monomer (i.e. dimethacrylate) that infiltrates and disperses the nanogel particles. Due to the presence of RAFT functionality and the fact that all initiating sites are initially located within the nanogel structure, gelation can be delayed by sequencing the polymerization from the nanogel to the bulk matrix. During polymerization of a nanogel-filled resin system, a progressive delay of gelation conversion from about 2 % for conventional chain growth polymerization to 18 % for the same monomer containing 20 wt% nanogel additive was achieved. A significant delay of stress development was also observed with much lower final stress achieved with the nanogel-modified systems due to the change of network formation mechanics. Compared with the nanogel-free dimethacrylate control, which contained uniformly distributed free initiator, the flexural modulus and mechanical strength results were maintained for the photopolymers with nanogel contents greater than 10 wt%. There appears to be a critical interparticle spacing of the photo-reactive nanogel that provides effective photopolymerization while providing delayed gelation and substantial stress reduction. PMID:24348753

  15. Construction of a lithium ion transport network in cathode with lithiated bis(benzene sulfonyl)imide based single ion polymer ionomers

    NASA Astrophysics Data System (ADS)

    Pan, Qiyun; Zhang, Wenchao; Pan, Meize; Zhang, Baodan; Zeng, Danli; Sun, Yubao; Cheng, Hansong

    2015-06-01

    We demonstrate a novel method to construct a lithium ion transport network in cathode materials by replacing PVDF with lithiated poly(bis(4-carbonyl benzene sulfonyl)imide-co-bis(4-amino benzene sulfonyl)imide) as the binder. The single ion conducting polymer was synthesized via polycondensation of bis(4-carbonyl benzene sulfonyl)imide and bis(4-amino benzene sulfonyl)imide followed by lithium ion exchange. By blending the ionomers with LiFePO4 and acetylene carbon, the ionic network was well constructed, resulting in a maximum use of active cathode material inside the cathode. The membrane of the polymer electrolyte exhibits an ionic conductivity of 0.14 mS cm-1 at room temperature, a high ion transference number of 0.92 and a wide electrochemical window of 4.5 V (vs. Li+/Li). A lithium ion battery assembled with the single ion conducting polymer electrolyte delivers excellent performance at room temperature with various C-rates.

  16. In vivo and in vitro taste masking of ofloxacin and sustained release by forming interpenetrating polymer network beads.

    PubMed

    Rajesh, A Michael; Popat, Kiritkumar Mangaldas

    2017-02-01

    Drug-resin complexes (DRCs) of ofloxacin and ion-exchange resins (IERs) were prepared in different ratios of drug/IERs, that is, 1:1, 1:2 and 1:4 (w/w) and investigated for taste masking by in vivo and in vitro release studies. Human volunteers graded AD1:4 (DRC) as tasteless with an average value of 0.3 ± 0.03 and in vitro study showed that AD 1:4 released only 1.70 ± 0.86% of drug at salivary pH within 30s. Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (P-XRD) and differential scanning calorimetry (DSC) studies of AD 1:4 showed the change in the morphology of the drug, that is, from crystalline phase to amorphous phase during complex formation. The release of drug from AD 1:4 was completed within 30 min at gastric pH 1.2 and to extend the release time of drug at gastric pH, it was entrapped with different biopolymers, such as sodium alginate (SA) and sodium carboxymethyl cellulose (SCMC), in the presence of ferric chloride and glutaraldehyde (GA) to form interpenetrating polymer network (IPN) beads. FTIR studies revealed that IPN beads were crosslinked with Fe(3+ )and GA. The release of drug at gastric and intestinal pH was 14.53 ± 1.52% and 65.86 ± 1.29%, respectively, for a contact time of 10 h. The kinetics release study shows fickian diffusion for ionically crosslinked beads and zero-order release for GA crosslinking beads.

  17. Networks 90: Polymer Networks Group Meeting (10th) and IUPAC international Symposium on Polymer Networks (10th) Held in Jerusalem on 20-25 May 1990. Programme and Abstracts

    DTIC Science & Technology

    1990-05-25

    at the ambient temperatureI (T) and pressure (p); pu, is the "contribution’ of the network to u,; q is the degree of swelling, which equals 1i/ where...Antonio Rey and Walther Burcharda) a) Institute of Macromolecular Chemistry, University of Freiburg 7800 Freiburg, FRG b) Departimento di Quimica Fisica...Ingenieria Quimica , 12 de octubre 1842, 8000 Bahia Blanca, Argentina. P-36 BRANCHING KINETICS OF EPOXY POLYMERIZATION OF 1,4-BUTANEDIOL DIGLYCIDYL ETHER

  18. Parabolic dependence of material properties and cell behavior on the composition of polymer networks via simultaneously controlling crosslinking density and crystallinity.

    PubMed

    Cai, Lei; Wang, Shanfeng

    2010-10-01

    A systematic investigation was performed on regulating materials properties and cell behavior using hybrid networks composed of amorphous poly(propylene fumarate) (PPF) and three poly(epsilon-caprolactone) diacrylates (PCLDAs) with variance in crystallinity and melting temperature. Through controlling both crosslinking density and crystallinity in the photo-crosslinked PPF/PCLDA blends, mechanical properties could be tuned efficiently in a wide range. For PCLDA synthesized from a low-molecular weight PCL diol precursor with a low crystallinity and a low melting point, crosslinks could completely suppress crystalline domains over the composition range in the PPF/PCLDA networks. Consequently, tensile, shear, torsional, and compression moduli all increased with the composition of PPF or the crosslinking density continuously for amorphous PPF/PCLDA networks. For PCLDAs synthesized using two PCL diols with higher molecular weights, crystallinity remained for the PCLDA compositions between approximately 80% and 100%. Minimum moduli and tensile stress at break were found at the lowest required composition of PPF for suppressing crystallinity. Surface physicochemical properties and morphology of the crosslinked blend disks have been characterized and their capabilities of adsorbing proteins from cell culture medium have been determined. Using both mouse MC3T3-E1 cells and rat Schwann cell precursor line (SpL201) cells, cell responses to these polymer networks such as cell adhesion, spreading, and proliferation were found to be dramatically distinct on different polymer networks and demonstrated non-monotonic or parabolic dependence on the network composition, coincident with the composition dependence of the mechanical properties.

  19. Thermal Stability and Ablation Behavior of Modified Polydimethylsiloxane-Based Polyurethane Composites Reinforced with Polyhedral Oligomeric Silsesquioxane.

    PubMed

    Han, Zhongyou; Xi, Yukun; Kwon, Younghwan

    2016-02-01

    Series of polydimethylsiloxane (PDMS)-based polyurethane (PU)/polyhedral oligomeric silsesquioxane (POSS) composites are prepared using ether or polyether modified diol/polyol PDMS prepolymers, isophorone diisocyanate (IPDI) and either non-reactive or reactive POSS. The effect of POSS incorporated chemically or physically, number of ethylene oxide units and crosslinking on PDMS based PU is investigated in terms of thermal stability and ablation properties. The ablation property is measured using an oxyacetylene torch test, and the ablation rate is evaluated. The results show that POSS molecules make a considerable influence on the ablative resistance, because they act as protective silica forming precursors under oxyacetylene condition. POSS molecules, especially methyl POSS, in PU matrix leads to the formation of densely accumulated spherical silica layers on the top of the ablated surface, resulting in improved ablation resistance.

  20. Conformation Transformation Determined by Different Self-Assembled Phases in a DNA Complex with Cationic Polyhedral Oligomeric Silsesquioxane Lipid

    SciTech Connect

    Cui,L.; Chen, D.; Zhu, L.

    2008-01-01

    In this work, a novel cube-shaped cationic lipid based on the imidazolium salt of polyhedral oligomeric silsesquioxane (POSS) was complexed with double-stranded DNA. Because of the negative spontaneous curvature of the cationic POSS imidazolium lipid, an inverted hexagonal phase resulted above the melting point of POSS crystals. Depending on the competition between the crystallization of POSS molecules and the negative spontaneous curvature of cationic POSS imidazolium lipids, different self-assembled phase morphologies were obtained. A lamellar phase was obtained when the POSS crystallization was relatively slow. When the POSS crystallization was fast, an inverted hexagonal phase was obtained with POSS lamellar crystals grown in the interstitials of DNA cylinders. On the basis of a circular dichroism study, double-stranded DNA adopted the B-form helical conformation in the inverted hexagonal phase, whereas the helical conformation was largely destroyed in the lamellar phase.

  1. Preparation of highly hydrophobic cotton fabrics by modification with bifunctional silsesquioxanes in the sol-gel process

    NASA Astrophysics Data System (ADS)

    Przybylak, Marcin; Maciejewski, Hieronim; Dutkiewicz, Agnieszka

    2016-11-01

    The surface modification of cotton fabrics was carried out using two types of bifunctional fluorinated silsesquioxanes with different ratios of functional groups. The modification was performed either by one- or two-step process. Two methods, the sol-gel and the dip coating method were used in different configurations. The heat treatment and the washing process were applied after modification. The wettability of cotton fabric was evaluated by measuring water contact angles (WCA). Changes in the surface morphology were examined by scanning electron microscopy (SEM, SEM-LFD) and atomic force microscopy (AFM). Moreover, the modified fabrics were subjected to analysis of elemental composition of the applied coatings using SEM-EDS techniques. Highly hydrophobic textiles were obtained in all cases studied and one of the modifications resulted in imparting superhydrophobic properties. Most of impregnated textiles remained hydrophobic even after multiple washing process which shows that the studied modification is durable.

  2. Mesoporous silica nanoparticles with organo-bridged silsesquioxane framework as innovative platforms for bioimaging and therapeutic agent delivery.

    PubMed

    Du, Xin; Li, Xiaoyu; Xiong, Lin; Zhang, Xueji; Kleitz, Freddy; Qiao, Shi Zhang

    2016-06-01

    Mesoporous silica material with organo-bridged silsesquioxane frameworks is a kind of synergistic combination of inorganic silica, mesopores and organics, resulting in some novel or enhanced physicochemical and biocompatible properties compared with conventional mesoporous silica materials with pure Si-O composition. With the rapid development of nanotechnology, monodispersed nanoscale periodic mesoporous organosilica nanoparticles (PMO NPs) and organo-bridged mesoporous silica nanoparticles (MSNs) with various organic groups and structures have recently been synthesized from 100%, or less, bridged organosilica precursors, respectively. Since then, these materials have been employed as carrier platforms to construct bioimaging and/or therapeutic agent delivery nanosystems for nano-biomedical application, and they demonstrate some unique and/or enhanced properties and performances. This review article provides a comprehensive overview of the controlled synthesis of PMO NPs and organo-bridged MSNs, physicochemical and biocompatible properties, and their nano-biomedical application as bioimaging agent and/or therapeutic agent delivery system.

  3. V2O5/SiO2 surface inspired, silsesquioxane-derived oxovanadium complexes and their properties.

    PubMed

    Ohde, Christian; Brandt, Marcus; Limberg, Christian; Döbler, Jens; Ziemer, Burckhard; Sauer, Joachim

    2008-01-21

    Inspired by surface species proposed to occur on heterogeneous catalysts novel oxovanadium(v) silsesquioxanes were synthesised. Reaction of a T8-silsequioxane containing two geminal OH groups with O=V(O(i)Pr)3 led to a dinuclear compound where the geminal disiloxide functions of two silsesquioxanes are bridging two O=V(O(i)Pr) moieties (2). Formation of 2 shows that--in contrast to proposals made for silica surfaces--in molecular chemistry a bidentate coordination of geminal siloxides to one vanadium centre is not favourable. With the background that species being doubly anchored to a support have been suggested to play active roles on V2O5/SiO2 catalysts an anionic complex has been prepared where a divalent dioxovanadium unit replaces one Si corner of a (RSiO1.5)8, cube (a Si-OH function remains pending) (3). 3 has been intensely investigated by vibrational spectroscopy, and to support assignments not only of the v(V=O) bands but also of the v(V-O-Si) bands, whose positions are of interest in the area of heterogeneous catalysis, isotopic enrichment studies and DFT calculations have been performed. The corresponding investigations were aided by the synthesis and analysis of a silylated derivative of 3, 4. Moreover, with regard to their potential as structural and spectroscopic models all complexes were characterised by single crystal X-ray diffraction. Finally, 2 and 3 were tested as potential catalysts for the photooxidation of cyclohexane and benzene with O2. While 2 shows a slightly higher activity than vanadylacetylacetonate, 3 leads to significantly increased turnover numbers for the conversion of benzene to phenol.

  4. Model Network Polymers.

    DTIC Science & Technology

    1982-09-01

    effects in property rela- tions for stepwise p~lyfunctional polymerization," Macromolecules 13, 1063 (1980). 10. F. Lopez- Serrano , J. M. Castro, M. V...Engineering, University del Sur, Bahia Blanca , Argentina) David J. Yarusso, B.S. June, 1978 (currently Ph.D. candidate, Department of Chemical...Ph.D. July, 1980 (currently Associate Professor of Chemical Engineering, Universidad del Sur, Bahia Blanca , Argentina) Richard J. Rolando, M.S. July

  5. Functionalized chitosan/NIPAM (HEMA) hybrid polymer networks as inserts for ocular drug delivery: synthesis, in vitro assessment, and in vivo evaluation.

    PubMed

    Verestiuc, Liliana; Nastasescu, Oana; Barbu, Eugen; Sarvaiya, Indrajeetsinh; Green, Keith L; Tsibouklis, John

    2006-06-15

    A series of hybrid polymeric hydrogels, prepared by the reaction of acrylic acid-functionalized chitosan with either N-isopropylacrylamide or 2-hydroxyethyl methacrylate monomers, were synthesized, pressed into minitablets, and investigated for their ability to act as controlled release vehicles for ophthalmic drug delivery. For comparison, interpolymeric complex analogues synthesized using the same monomers and pure, unfunctionalized chitosan were examined by means of an identical characterization protocol. The effects of network structure and composition upon the swelling properties, adhesion behavior, and drug release characteristics were investigated. Comparative in vitro studies employing chloramphenicol, atropine, norfloxacin, or pilocarpine informed the selection of drug-specific carrier compositions for the controlled delivery of these compounds. In addition, in vivo (rabbit model) experiments involving the delivery of pilocarpine indicated that chitosan-based hybrid polymer networks containing 2-hydroxyethyl methacrylate are useful carriers for the delivery of this therapeutic agent.

  6. Effect of polyacrylonitrile on triethylene glycol diacetate-2-propenoic acid butyl ester gel polymer electrolytes with interpenetrating crosslinked network for flexible lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Qiujun; Song, Wei-Li; Fan, Li-Zhen; Shi, Qiao

    2015-11-01

    A new flexible gel polymer electrolytes (GPE) with interpenetrating cross-linked network is fabricated by blending long-chain polyacrylonitrile (PAN) polymer matrix and short-chain triethylene glycol diacetate-2-propenoic acid butyl ester (TEGDA-BA) framework, with the purpose of enhancing the mechanical stability of the GPE frameworks via synergistic effects of the linear polymers and crosslinked monomers. The as fabricated frameworks enable the liquid electrolytes to be firmly entrapped in the polymeric matrices, which significantly improves the mechanical bendability and interface stability of the resultant GPE. The GPE with 5 wt% PAN exhibits high ionic conductivity up to 5.9 × 10-3 S cm-1 at 25 °C with a stable electrochemical window observed (>5.0 V vs. Li/Li+). The Li|GPE|LiFePO4 half cells demonstrate remarkably stable capacity retention and rate ability during cycling tests. As expected, the LiFePO4|GPE|Li4Ti5O12 full cells also exhibit discharge capacity of 125.2 mAh g-1 coupled with high columbic efficiency greater than 98% after 100 cycles. The excellent mechanical flexibility and charge/discharge performance suggest that the GPE holds great application potential in flexible LIBs.

  7. Efficient ibuprofen delivery from anhydrous semisolid formulation based on a novel cross-linked silicone polymer network: an in vitro and in vivo study.

    PubMed

    Aliyar, Hyder; Huber, Robert; Loubert, Gary; Schalau, Gerald

    2014-07-01

    The use of silicone as a primary polymer in topical semisolid pharmaceutical formulations is infrequent. Recent development of novel silicone materials provides an opportunity to investigate their drug delivery efficiencies. In this study, an anhydrous semisolid formulation was prepared using a novel cross-linked silicone polymer network swollen in isododecane. Similar formulations were prepared using petrolatum, an acrylic, or a cellulose polymer. All formulations contained 5% ibuprofen (IBP). In vitro permeability was evaluated for all formulations and a commercial product using human cadaver epidermis. The silicone formulation delivered IBP more efficiently than all other formulations in terms of flux, cumulative amount, and percent drug release. The silicone formulation showed the maximum flux of 85.9 μg . cm(-2) . h(-1) and a cumulative IBP release of 261.6 μg in 8 h, whereas the benchmark showed 20.1 μg . cm(-2) . h(-1) and 30.9 μg, respectively. An in vivo study conducted on rats showed calculated blood AUCs of 59.2 and 17.6 μg . h/g (p < 0.003) for the silicone formulation and the benchmark, respectively. The IBP in excised rat skin was 264 ± 59 μg/g for the silicone formulation and 102 ± 5 μg/g for the benchmark. The results obtained from the in vitro and in vivo studies demonstrate efficient topical IBP delivery by the silicone formulation.

  8. Nuclear Instruments and Methods in Physics Research. Section B; Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy

    NASA Technical Reports Server (NTRS)

    Singh, Jag J.; Pater, Ruth H.; Eftekhari, Abe

    1998-01-01

    Thermoset and thermoplastic polyimides have complementary physical/mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. It is expected that a combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPNs) of thermoset LaRC(Trademark)-RP46 and thermoplastic LARC(Trademark)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0: 100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical/mechanical properties. As expected, positronium atoms are not formed in these samples. The second life time component has been used to infer the positron trap dimensions. The "free volume" goes through a minimum at about 50:50 ratio, suggesting that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples have been discussed in this paper.

  9. Strain-induced crystallization in elastomeric polymer networks prepared in solution and sol-gel derived high-temperature organic-inorganic hybrid materials

    NASA Astrophysics Data System (ADS)

    Premachandra, Jagath Kumara

    Cross-linking polymer chains in solution should bring about fewer inter-chain entanglements in the resulting network. The subsequent drying of this network should compress the chains into a "super-contracted" state. The opposing effects of these changes on strain-induced crystallization in cis-1,4-polyisoprene networks formed in solution were investigated. Higher elongations were required to achieve strain-induced crystallinity in the networks prepared at higher dilutions, suggesting that in this regard the compressed states of the chains was more important than their reduced entangling. The constrained-junction theory was applied to strain-induced crystallization in the above networks. The stress-strain isotherms generated from this theory were in satisfactory agreement with experiment. It was found that the constraint parameter kappa decreases with increase in dilution during cross-linking mainly due to the fact that cross-linking in solution decreases chain interpenetration. The dependence of hydrolysis and condensation of gamma-ureidopropyltrimethoxysilane on pH in the water-methanol system at 23sp°C was investigated by FTIR spectroscopy. Quantitative analysis of rates of hydrolysis showed that gamma-ureidopropyltrimethoxysilane is most stable in the water-methanol system at pH 7.7. The rate of overall condensation of silanols produced by the hydrolysis was qualitatively analyzed. These silanol groups are relatively more stable around pH 4.87. The mechanical properties, thermal stability and water absorption of high-temperature sulfopolybenzobisthiazole-silica hybrid materials were investigated. The use of a bonding agent N,N-diethylaminopropyltrimethoxysilane facilitated the interfacial bonding between the organic and inorganic phases in these materials prepared through the sol-gel process. Tensile modulus, thermal stability and the resistant to water absorption were increased with increase in silica content in the resulting composites

  10. Ceramic microparticles and capsules via microfluidic processing of a preceramic polymer

    PubMed Central

    Ye, Congwang; Chen, Anthony; Colombo, Paolo; Martinez, Carlos

    2010-01-01

    We have developed a robust technique to fabricate monodispersed solid and porous ceramic particles and capsules from single and double emulsion drops composed of silsesquioxane preceramic polymer. A microcapillary microfluidic device was used to generate the monodispersed drops. In this device, two round capillaries are aligned facing each other inside a square capillary. Three fluids are needed to generate the double emulsions. The inner fluid, which flows through the input capillary, and the middle fluid, which flows through the void space between the square and inner fluid capillaries, form a coaxial co-flow in a direction that is opposite to the flow of the outer fluid. As the three fluids are forced through the exit capillary, the inner and middle fluids break into monodispersed double emulsion drops in a single-step process, at rates of up to 2000 drops s−1. Once the drops are generated, the silsesquioxane is cross-linked in solution and the cross-linked particles are dried and pyrolysed in an inert atmosphere to form oxycarbide glass particles. Particles with diameters ranging from 30 to 180 µm, shell thicknesses ranging from 10 to 50 µm and shell pore diameters ranging from 1 to 10 µm were easily prepared by changing fluid flow rates, device dimensions and fluid composition. The produced particles and capsules can be used in their polymeric state or pyrolysed to ceramic. This technique can be extended to other preceramic polymers and can be used to generate unique core–shell multimaterial particles. PMID:20484226

  11. Polymer films

    DOEpatents

    Granick, Steve; Sukhishvili, Svetlana A.

    2004-05-25

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  12. Polymer films

    DOEpatents

    Granick, Steve; Sukhishvili, Svetlana A.

    2008-12-30

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  13. Polymer stabilization of the smectic C-alpha* liquid crystal phase—Over tenfold thermal stabilization by confining networks of photo-polymerized reactive mesogens

    SciTech Connect

    Labeeb, A.; Gleeson, H. F.; Hegmann, T.

    2015-12-07

    The smectic C*-alpha (SmC{sub α}*) phase is one of the sub-phases of ferroelectric liquid crystals that has drawn much interest due to its electro-optical properties and ultrafast switching. Generally observed above the ferroelectric SmC* phase in temperature, the SmC{sub α}* commonly shows only very narrow phase temperature range of a few degree Celsius. To broaden the SmC{sub α}* phase, polymer stabilization was investigated for thermal phase stabilization. Two different reactive monomers were tested in three mixtures, and all three broadened the temperature range of the SmC{sub α}* phase from 3 °C to 39 °C. The current reversal method was used to determine the phase existence versus temperature. Moreover, the texture and network structure was studied by polarized optical microscopy and scanning electron microscopy, with the latter revealing the confinement of the smectic layer structure within the porous polymer network.

  14. Silver nanowire percolation network soldered with graphene oxide at room temperature and its application for fully stretchable polymer light-emitting diodes.

    PubMed

    Liang, Jiajie; Li, Lu; Tong, Kwing; Ren, Zhi; Hu, Wei; Niu, Xiaofan; Chen, Yongsheng; Pei, Qibing

    2014-02-25

    Transparent conductive electrodes with high surface conductivity, high transmittance in the visible wavelength range, and mechanical compliance are one of the major challenges in the fabrication of stretchable optoelectronic devices. We report the preparation of a transparent conductive electrode (TCE) based on a silver nanowire (AgNW) percolation network modified with graphene oxide (GO). The monatomic thickness, mechanical flexibility, and strong bonding with AgNWs enable the GO sheets to wrap around and solder the AgNW junctions and thus dramatically reduce the inter-nanowire contact resistance without heat treatment or high force pressing. The GO-soldered AgNW network has a figure-of-merit sheet resistance of 14 ohm/sq with 88% transmittance at 550 nm. Its storage stability is improved compared to a conventional high-temperature annealed AgNW network. The GO-soldered AgNW network on polyethylene terephthalate films was processed from solutions using a drawdown machine at room temperature. When bent to 4 mm radius, its sheet resistance was increased by only 2-3% after 12,000 bending cycles. GO solder can also improve the stretchability of the AgNW network. Composite TCE fabricated by inlaying a GO-soldered AgNW network in the surface layer of polyurethane acrylate films is stretchable, by greater than 100% linear strain without losing electrical conductivity. Fully stretchable white polymer light-emitting diodes (PLEDs) were fabricated for the first time, employing the stretchable TCE as both the anode and cathode. The PLED can survive after 100 stretching cycles between 0 and 40% strain and can be stretched up to 130% linear strain at room temperature.

  15. Synthesis of polyhedral oligomeric silsesquioxane (POSS) functionalized carbon nanotubes for improved dispersion in polyurethane films

    NASA Astrophysics Data System (ADS)

    Kou, Xiaonan

    Carbon nanotube (CNT) polymer nanocomposites are promising advanced materials. These materials exhibit the advantages of traditional polymeric materials, such as being light weight and easy to process, combined with the potential to exhibit enhanced mechanical, thermal and electrical properties compared to pure polymers. To achieve substantial improvement of composite properties at low CNT loading, uniform dispersion of CNTs in the polymer matrix and strong CNT-polymer interfacial interaction are needed. However, it is difficult to achieve adequate dispersion and interfacial interactions due to the inert nature of CNTs. In this project, polyhedral oligomeric silsequioxane (POSS) will be used as a dispersing agent for multi-walled carbon nanotubes (MWNTs) in polyurethane (PU) matrices. This dissertation consists of six chapters. Chapter I provides a detailed introduction of the fundamental knowledge of CNTs, PU, and POSS. At the end of this chapter, the motivation and rationale of this research are given. Chapter II establishes the overall goal and specific objectives of this research. Chapter III describes the synthesis and characterization of three POSS modified CNTs and one organosilane modified CNT. Grafting efficiency of the different grafted molecules are calculated and compared. Chapter IV discusses the dispersion behavior of four covalently modified CNTs in both solvents and PU matrices. Differences in dispersion behaviors of the modified CNTs are correlated to the solubility parameters of the grafting molecules and the surface structures of modified CNTs. Chapter V provides further discussion of the dispersion of POSS and silane modified CNTs by reviewing the assessment of the physical properties of PU composites containing the modified CNTs. Morphological, thermal, mechanical and electrical properties are used to estimate the interactions of the modified CNTs with the PU matrix. Chapter VI explores the function of the trisilanolphenyl POSS lithium salt

  16. Styrene-butadiene-styrene Tri-block Copolymers Modified wit Polyhedral Oligomeric Silsesquioxanes

    DTIC Science & Technology

    2006-05-31

    morphology.1-6 Polymer nano -composites are a new and active research area in the field of block copolymers. Block copolymers reinforced by various nano -sized...fillers have been prepared and studied; layered silicates-based nano -composites have drawn the most attention thus far. 7- 9 Although domain...morphology is not strongly influenced by the blending of layered- silicates, these nano -reinforced block copolymers have shown promising property enhancements

  17. Preparation of Composite Fluoropolymers with Enhanced Dewetting Using Fluorinated Silsesquioxanes as Drop-In Modifiers (Preprint)

    DTIC Science & Technology

    2010-02-17

    blend formulations have potential use as hydro- and oleophobic materials for seals, fibers, and coatings. 15. SUBJECT TERMS 16. SECURITY...This work demonstred that optimized F-POSS PFCB aryl ether polymer blend formulations have potential use as hydro- and oleophobic materials for seals... oleophobic 20 properties. There are numerous examples of materials that mimic naturally evolved biological systems, albeit they are mostly limited to

  18. Effect of Polymer Gate Dielectrics on Charge Transport in Carbon Nanotube Network Transistors: Low-k Insulator for Favorable Active Interface.

    PubMed

    Lee, Seung-Hoon; Xu, Yong; Khim, Dongyoon; Park, Won-Tae; Kim, Dong-Yu; Noh, Yong-Young

    2016-11-30

    Charge transport in carbon nanotube network transistors strongly depends on the properties of the gate dielectric that is in direct contact with the semiconducting carbon nanotubes. In this work, we investigate the dielectric effects on charge transport in polymer-sorted semiconducting single-walled carbon nanotube field-effect transistors (s-SWNT-FETs) by using three different polymer insulators: A low-permittivity (εr) fluoropolymer (CYTOP, εr = 1.8), poly(methyl methacrylate) (PMMA, εr = 3.3), and a high-εr ferroelectric relaxor [P(VDF-TrFE-CTFE), εr = 14.2]. The s-SWNT-FETs with polymer dielectrics show typical ambipolar charge transport with high ON/OFF ratios (up to ∼10(5)) and mobilities (hole mobility up to 6.77 cm(2) V(-1) s(-1) for CYTOP). The s-SWNT-FET with the lowest-k dielectric, CYTOP, exhibits the highest mobility owing to formation of a favorable interface for charge transport, which is confirmed by the lowest activation energies, evaluated by the fluctuation-induced tunneling model (FIT) and the traditional Arrhenius model (EaFIT = 60.2 meV and EaArr = 10 meV). The operational stability of the devices showed a good agreement with the activation energies trend (drain current decay ∼14%, threshold voltage shift ∼0.26 V in p-type regime of CYTOP devices). The poor performance in high-εr devices is accounted for by a large energetic disorder caused by the randomly oriented dipoles in high-k dielectrics. In conclusion, the low-k dielectric forms a favorable interface with s-SWNTs for efficient charge transport in s-SWNT-FETs.

  19. Wavelength control of random polymer fiber laser based on adaptive disorder.

    PubMed

    Hu, Zhijia; Gao, Pengfei; Xie, Kang; Liang, Yunyun; Jiang, Haiming

    2014-12-15

    We demonstrate the realization of two different kinds of random polymer optical fiber lasers to control the random lasing wavelength by changing the disorder of polymer optical fibers (POFs). One is a long-range disorder POF based on copolymer refractive-index inhomogeneity, and the other is a short-range disorder POF based on polyhedral oligomeric silsesquioxanes scattering. By end pumped both disorder POFs, the coherent random lasing for both is observed. Meanwhile, the random lasing wavelength of the short-range disorder POF because of a small scattering mean-free path has been found to be blue shifted with respect to the long-range disorder POF, which will give a way to control the random lasing wavelength.

  20. Physical organic chemistry of supramolecular polymers.

    PubMed

    Serpe, Michael J; Craig, Stephen L

    2007-02-13

    Unlike the case of traditional covalent polymers, the entanglements that determine properties of supramolecular polymers are defined by very specific, intermolecular interactions. Recent work using modular molecular platforms to probe the mechanisms underlying mechanical response of supramolecular polymers is reviewed. The contributions of supramolecular kinetics, thermodynamics, and conformational flexibility to supramolecular polymer properties in solutions of discrete polymers, in networks, and at interfaces, are described. Molecule-to-material relationships are established through methods reminiscent of classic physical organic chemistry.

  1. Bio-based Interpenetrating Network Polymer Composites from Locust Sawdust as Coating Material for Environmentally Friendly Controlled-Release Urea Fertilizers.

    PubMed

    Zhang, Shugang; Yang, Yuechao; Gao, Bin; Wan, Yongshan; Li, Yuncong C; Zhao, Chenhao

    2016-07-20

    A novel polymer-coated nitrogen (N) fertilizer was developed using bio-based polyurethane (PU) derived from liquefied locust sawdust as the coating material. The bio-based PU was successfully coated on the surface of the urea fertilizer prills to form polymer-coated urea (PCU) fertilizer for controlled N release. Epoxy resin (EP) was also used to further modify the bio-based PU to synthesize the interpenetrating network (IPN), enhancing the slow-release properties of the PCU. The N release characteristics of the EP-modified PCU (EMPCU) in water were determine at 25 °C and compared to that of PCU and EP-coated urea (ECU). The results showed that the EP modification reduced the N release rate and increased the longevity of the fertilizer coated with bio-based PU. A corn growth study was conducted to further evaluate the filed application of the EMPCU. In comparison to commercial PCU and conventional urea fertilizer, EMPCU was more effective and increased the yield and total dry matter accumulation of the corn. Findings from this work indicated that bio-based PU derived from sawdust can be used as coating materials for PCU, particularly after EP modification. The resulting EMPCU was more environmentally friendly and cost-effective than conventional urea fertilizers coated by EP.

  2. On the origin of Gaussian network theory in the thermo/chemo-responsive shape memory effect of amorphous polymers undergoing photo-elastic transition

    NASA Astrophysics Data System (ADS)

    Lu, Haibao; Huang, Wei Min; Leng, Jinsong

    2016-06-01

    Amorphous polymers are normally isotropic in their physical properties, however, upon stress their structural randomness is disturbed and they become anisotropic. There is a close connection between the optical anisotropy and the elastic (or mechanical) anisotropy, since both are related to the type of symmetry exhibited by the molecular structure. On the origin of Gaussian network theory, a phenomenological constitutive framework was proposed to study the photo-elastic transition and working mechanism of the thermo-/chemo-responsive shape-memory effect (SME) in amorphous shape memory polymers (SMPs). Optically refractive index was initially employed to couple the stress, strain and the anisotropy of the random link in macromolecule chain. Based on the Arrhenius law, a constitutive framework was then applied for the temperature dependence of optical (or elastic or mechanical) anisotropy according to the fictive temperature parameter. Finally, the phenomenological photo-elastic model was proposed to quantitatively identify the influential factors behind the thermo-/chemo-responsive SME in SMPs, of which the shape recovery behavior is predicted and verified by the available experimental data reported in the literature.

  3. Optimization of a polymer composite employing molecular mechanic simulations and artificial neural networks for a novel intravaginal bioadhesive drug delivery device.

    PubMed

    Ndesendo, Valence M K; Pillay, Viness; Choonara, Yahya E; du Toit, Lisa C; Kumar, Pradeep; Buchmann, Eckhart; Meyer, Leith C R; Khan, Riaz A

    2012-01-01

    This study aimed at elucidating an optimal synergistic polymer composite for achieving a desirable molecular bioadhesivity and Matrix Erosion of a bioactive-loaded Intravaginal Bioadhesive Polymeric Device (IBPD) employing Molecular Mechanic Simulations and Artificial Neural Networks (ANN). Fifteen lead caplet-shaped devices were formulated by direct compression with the model bioactives zidovudine and polystyrene sulfonate. The Matrix Erosion was analyzed in simulated vaginal fluid to assess the critical integrity. Blueprinting the molecular mechanics of bioadhesion between vaginal epithelial glycoprotein (EGP), mucin (MUC) and the IBPD were performed on HyperChem 8.0.8 software (MM+ and AMBER force fields) for the quantification and characterization of correlative molecular interactions during molecular bioadhesion. Results proved that the IBPD bioadhesivity was pivoted on the conformation, orientation, and poly(acrylic acid) (PAA) composition that interacted with EGP and MUC present on the vaginal epithelium due to heterogeneous surface residue distributions (free energy= -46.33 kcalmol(-1)). ANN sensitivity testing as a connectionist model enabled strategic polymer selection for developing an IBPD with an optimally prolonged Matrix Erosion and superior molecular bioadhesivity (ME = 1.21-7.68%; BHN = 2.687-4.981 N/mm(2)). Molecular modeling aptly supported the EGP-MUC-PAA molecular interaction at the vaginal epithelium confirming the role of PAA in bioadhesion of the IBPD once inserted into the posterior fornix of the vagina.

  4. Adsorption of ammonium and phosphate by feather protein based semi-interpenetrating polymer networks hydrogel as a controlled-release fertilizer.

    PubMed

    Su, Yuan; Liu, Jia; Yue, Qinyan; Li, Qian; Gao, Baoyu

    2014-01-01

    A new feather protein-grafted poly(potassium acrylate)/polyvinyl alcohol (FP-g-PKA/PVA) semi-interpenetrating polymer networks (semi-IPNs) hydrogel was produced through graft copolymerization with FP as a basic macromolecular skeletal material, acrylic acid as a monomer and PVA as a semi-IPNs polymer. The adsorption of ammonium and phosphate ions from aqueous solution using the new hydrogel as N and P controlled-release fertilizer with water-retention capacity was studied. The effects of pH value, concentration, contact time and ion strength on NH4+ and PO3-4 removal by FP-g-PKA/PVA semi-IPNs hydrogel were investigated using batch adsorption experiments. The results indicated that the hydrogel had high adsorption capacities and fast adsorption rates for NH4+ and PO3-4 in wide pH levels ranging from 4.0 to 9.0. Kinetic analysis presented that both NH4+ and PO3-4 removal were closely fitted with the pseudo-second-order model. Furthermore, the adsorption isotherms of hydrogel were best represented by the Freundlich model. The adsorption-desorption experimental results showed the sustainable stability of FP-g-PKA/PVA semi-IPNs hydrogel for NH4+ and PO3-4 removal. Overall, FP-g-PKA/PVA could be considered as an efficient material for the removal and recovery of nitrogen and phosphorus with the agronomic reuse as a fertilizer.

  5. Interaction of SF6 and O2 plasma with porous poly phenyl methyl silsesquioxane low-κ films

    NASA Astrophysics Data System (ADS)

    Cherunilam, J. F.; Rajani, K. V.; Byrne, C.; Heise, A.; McNally, P. J.; Daniels, S.

    2015-04-01

    A reduction in the κ-value of dielectric materials is of great interest today as it leads to the reduction of resistance-capacitance delays and parasitic capacitances within integrated circuits, thereby improving device performance. We have recently reported our studies on the great potential of the Poly phenyl methyl silsesquioxane (PMSQ) low-κ films (κ = 2.7  ±  0.2) for interlayer dielectric applications. Here we report on the deposition and characterisation of porous PMSQ thin films using Heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin as the porogen. A reduction in the κ-value of the films was achieved as a function of the increase in porogen loading in the film. The removal of the thermally liable porogen material from the hybrid films was studied using thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). The change in density as a function of the porosity was studied using x-ray reflectivity techniques. The interaction of the films with pure SF6 and O2 plasmas was studied and the surface modification that occurs in the films as a result of the interaction was studied using FTIR and x-ray photoelectron spectroscopy. A change in the κ-value of the films was observed after plasma treatment which is attributed to the chemical modification of the film surface due to plasma interaction.

  6. Highly stable nanofluid based on polyhedral oligomeric silsesquioxane-decorated graphene oxide nanosheets and its enhanced electro-responsive behavior

    NASA Astrophysics Data System (ADS)

    Li, Yizhuo; Guan, Yanqing; Liu, Yang; Yin, Jianbo; Zhao, Xiaopeng

    2016-05-01

    Graphene oxide (GO) shows potential as an anisotropic nanofiller or a dispersed phase of electro-responsive electrorheological (ER) nanofluid due to its small size and high aspect ratio. But it is difficult to disperse GO in non-polar oil due to the hydrophilic nature of GO and thus the resulting fluid is often subject to dispersion instability and low ER effect. These disadvantages largely limit the real application of GO-based ER nanofluid. In this paper, we develop the polyhedral oligomeric silsesquioxane (POSS)-decorated GO (POSS-GO) nanosheets and demonstrate that decorating with POSS overcomes the dispersion instability of GO in silicone oil and enhances the ER effect. The morphology and structure of samples are characterized by atomic force microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and x-ray photoelectronic spectroscopy. The results show that the POSS-GO nanosheets are ultrathin with ∼3 nm thickness and have good compatibility with silicone oil and, as a result, the nanofluid of POSS-GO nanosheets in silicone oil shows high dispersion stability. After standing for one year at room temperature, no sedimentation occurs. Under an external electric field, the ER efficiency of the POSS-GO nanofluid is ten times as high as that of the pure GO fluid. This enhanced electro-responsive behavior is related to the fact that decorating with POSS partly reduces the GO and compresses the dielectrophoretic effect of the negatively charged pure GO fluid.

  7. Fabrication of boronate-decorated polyhedral oligomeric silsesquioxanes grafted cotton fiber for the selective enrichment of nucleosides in urine.

    PubMed

    Gao, Li; Wei, Yinmao

    2016-06-01

    Various cotton fiber based boronate-affinity adsorbents are recently developed for the sample pretreatment of cis-diol-containing biomolecules, but most do not have efficient capacity due to limited binding sites on the surface of cotton fibers. To increase the density of boronate groups on the surface of cotton fiber, polyhedral oligomeric silsesquioxanes were used to modify cotton fiber to provide plentiful reactive sites for subsequent functionalization with 4-formylphenylboronic acid. The new adsorbent showed special recognition ability towards cis-diols and high adsorption capacity (175 μg/g for catechol, 250 μg/g for dopamine, 400 μg/g for adenosine). The in-pipette-tip solid-phase extraction was investigated under different conditions, including pH and ionic strength of solution, adsorbent amount, pipette times, washing solvent, and elution solvent. The in-pipette-tip solid-phase extraction coupled with high-performance liquid chromatography was used to analyze four nucleosides in urine samples. Under the optimal extraction conditions, the detection limits were determined to be between 5.1 and 6.1 ng/mL (S/N  =  3), and the linearity ranged from 20 to 500 ng/mL for these analytes. The accuracy of the analytical method was examined by studying the relative recoveries of analytes in real urine samples with recoveries varying from 83 to 104% (RSD = 3.9-10.2%, n = 3).

  8. Mass-fractal growth in niobia/silsesquioxane mixtures: a small-angle X-ray scattering study

    PubMed Central

    Besselink, Rogier; ten Elshof, Johan E.

    2014-01-01

    The nucleation and growth of niobium pentaethoxide (NPE)-derived clusters in ethanol, through acid-catalyzed hydrolysis/condensation in the presence and absence of the silsesquioxane 1,2-bis(triethoxysilyl)ethane (BTESE), was monitored at 298–333 K by small-angle X-ray scattering. The data were analyzed with a newly derived model for polydisperse mass-fractal-like structures. At 298–313 K in the absence of BTESE the data indicated the development of relatively monodisperse NPE-derived structures with self-preserving polydispersity during growth. The growth exponent was consistent with irreversible diffusion-limited cluster agglomeration. At 333 K the growth exponent was characteristic for fast-gelling reaction-limited cluster agglomeration. The reaction yielded substantially higher degrees of polydispersity. In the presence of BTESE the growth exponents were substantially smaller. The smaller growth exponent in this case is not consistent with irreversible Smoluchowski-type agglomeration. Instead, reversible Lifshitz–Slyozov-type agglomeration seems to be more consistent with the experimental data. PMID:25294980

  9. Physical properties of a high molecular weight hydroxyl-terminated polydimethylsiloxane modified castor oil based polyurethane/epoxy interpenetrating polymer network composites

    NASA Astrophysics Data System (ADS)

    Chen, Shoubing; Wang, Qihua; Wang, Tingmei

    2011-06-01

    A series of polyurethane (PU)/epoxy resin (EP) graft interpenetrating polymer network (IPN) composites modified by a high molecular weight hydroxyl-terminated polydimethylsiloxane (HTPDMS) were prepared. The effects of HTPDMS content on the phase structure, damping properties and the glass transition temperature ( Tg) of the HTPDMS-modified PU/EP IPN composites were studied by scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA). Thermogravimetric analysis (TGA) showed that the thermal decomposition temperature of the composites increased with the increase of HTPDMS content. The tensile strength and impact strength of the IPN composites were also significantly improved, especially when the HTPDMS content was 10%. The modified IPN composites were expected to be used as structural damping materials in the future.

  10. Pore network modeling to explore the effects of compression on multiphase transport in polymer electrolyte membrane fuel cell gas diffusion layers

    NASA Astrophysics Data System (ADS)

    Fazeli, Mohammadreza; Hinebaugh, James; Fishman, Zachary; Tötzke, Christian; Lehnert, Werner; Manke, Ingo; Bazylak, Aimy

    2016-12-01

    Understanding how compression affects the distribution of liquid water and gaseous oxygen in the polymer electrolyte membrane fuel cell gas diffusion layer (GDL) is vital for informing the design of improved porous materials for effective water management strategies. Pore networks extracted from synchrotron-based micro-computed tomography images of compressed GDLs were employed to simulate liquid water transport in GDL materials over a range of compression pressures. The oxygen transport resistance was predicted for each sample under dry and partially saturated conditions. A favorable GDL compression value for a preferred liquid water distribution and oxygen diffusion was found for Toray TGP-H-090 (10%), yet an optimum compression value was not recognized for SGL Sigracet 25BC. SGL Sigracet 25BC exhibited lower transport resistance values compared to Toray TGP-H-090, and this is attributed to the additional diffusion pathways provided by the microporous layer (MPL), an effect that is particularly significant under partially saturated conditions.

  11. An electronic-nose sensor node based on a polymer-coated surface acoustic wave array for wireless sensor network applications.

    PubMed

    Tang, Kea-Tiong; Li, Cheng-Han; Chiu, Shih-Wen

    2011-01-01

    This study developed an electronic-nose sensor node based on a polymer-coated surface acoustic wave (SAW) sensor array. The sensor node comprised an SAW sensor array, a frequency readout circuit, and an Octopus II wireless module. The sensor array was fabricated on a large K(2) 128° YX LiNbO3 sensing substrate. On the surface of this substrate, an interdigital transducer (IDT) was produced with a Cr/Au film as its metallic structure. A mixed-mode frequency readout application specific integrated circuit (ASIC) was fabricated using a TSMC 0.18 μm process. The ASIC output was connected to a wireless module to transmit sensor data to a base station for data storage and analysis. This sensor node is applicable for wireless sensor network (WSN) applications.

  12. Structure property relationships in polymer blends and composites. Part I. Polymer/POSS composites. Part II. Poly(ethylene terephthalate) ionomer/polyamide 6 blends. Part III. Elastomer/boron nitride composites

    NASA Astrophysics Data System (ADS)

    Iyer, Subramanian

    Multiphase polymer systems are an increasingly important technical area of polymer science. By definition, a multiphase system is one that has two or more distinct phases. From the standpoint of commercial applications and developments, polymer blending represents one of the easiest ways to achieve properties not available in individual materials. This work discusses the structure property relationships in polymer certain blends and composites. Polymer/polyhedral oligomeric silsesquioxanes (POSSRTM) blends and copolymers have gained significant attention in the last decade due the unique properties of the inorganic-organic hybrid structure of POSS. The majority of the research in polymer/POSS has been in the form of copolymers and thermosets. The criteria for the reinforcement of polymers using POSS as a filler material is not been discussed in literature. Part I of the thesis will highlight the effect of blending POSS with different polymers and discuss the rules for reinforcement of polymers when using POSS as a filler material. Part II of the thesis will discuss the structure property relationships in poly(ethylene terephthalate) ionomer/polyamide 6 blends. Part III will discuss the control of coefficient of thermal expansion of elastomers using boron nitride as a filler material.

  13. Three-dimensional activated graphene network-sulfonate-terminated polymer nanocomposite as a new electrode material for the sensitive determination of dopamine and heavy metal ions.

    PubMed

    Yuan, Xiaoyan; Zhang, Yijia; Yang, Lu; Deng, Wenfang; Tan, Yueming; Ma, Ming; Xie, Qingji

    2015-03-07

    We report here that three-dimensional activated graphene networks (3DAGNs) are a better matrix to prepare graphene-polymer nanocomposites for sensitive electroanalysis than two-dimensional graphene nanosheets (2DGNs). 3DAGNs were synthesized in advance by the direct carbonization and simultaneous chemical activation of a cobalt ion-impregnated D113-type ion exchange resin, which showed an interconnected network structure and a large specific surface area. Then, the 3DAGN-sulfonate-terminated polymer (STP) nanocomposite was prepared via the in situ chemical co-polymerization of m-aminobenzene sulfonic acid and aniline in the presence of 3DAGNs. The 3DAGN-STP nanocomposite can adsorb dopamine (DA) and heavy metal ions, which was confirmed by quartz crystal microbalance studies. The 3DAGN-STP modified glassy carbon electrode (GCE) was used for the electrochemical detection of DA in the presence of ascorbic acid and uric acid, with a linear response range of 0.1-32 μM and a limit of detection of 10 nM. In addition, differential pulse voltammetry was used for the simultaneous determination of Cd(2+) and Pb(2+) at the 3DAGN-STP/GCE further modified with a bismuth film, exhibiting linear response ranges of 1-70 μg L(-1) for Cd(2+) and 1-80 μg L(-1) for Pb(2+) with limits of detection of 0.1 μg L(-1) for Cd(2+) and 0.2 μg L(-1) for Pb(2+). Because the 3DAGN-STP can integrate the advantages of 3DAGNs with STPs, the 3DAGN-STP/GCE was more sensitive than the bare GCE, 3DAGN/GCE, and 2DGN-STP/GCE for the determination of DA and heavy metal ions.

  14. Porous polymer media

    DOEpatents

    Shepodd, Timothy J.

    2002-01-01

    Highly crosslinked monolithic porous polymer materials for chromatographic applications. By using solvent compositions that provide not only for polymerization of acrylate monomers in such a fashion that a porous polymer network is formed prior to phase separation but also for exchanging the polymerization solvent for a running buffer using electroosmotic flow, the need for high pressure purging is eliminated. The polymer materials have been shown to be an effective capillary electrochromatographic separations medium at lower field strengths than conventional polymer media. Further, because of their highly crosslinked nature these polymer materials are structurally stable in a wide range of organic and aqueous solvents and over a pH range of 2-12.

  15. Carbon Nanofiber Reinforced Polymers

    DTIC Science & Technology

    2006-01-01

    2006 2. REPORT TYPE 3. DATES COVERED 00-00-2006 to 00-00-2006 4. TITLE AND SUBTITLE Carbon Nanofiber Reinforced Polymers 5a. CONTRACT NUMBER 5b...REVIEW Carbon Nanofiber Reinforced Polymers J.N. Baucom, A. Rohatgi, W.R. Pogue III, and J.P. Thomas Materials Science and Technology Division...of mass-produced and inexpensive, discontinuous carbon nanofibers to create a percolated fiber network within a polymeric matrix that will result in

  16. Directed Self-assembly of Nanoparticles at the Polymer Surface by Highly Compressible Supercritical Carbon Dioxide

    SciTech Connect

    M Asada; P Gin; M Endoh; S Satija; T Taniguchi; T Koga

    2011-12-31

    We report a versatile route for self-assembly of polymer-soluble nanoparticles at the polymer surface using highly compressible supercritical carbon dioxide (scCO{sub 2}). Polystyrene and poly(methyl methacrylate)-based nanocomposite thin films with functionalized polyhedral oligomeric silsesquioxane and phenyl C{sub 61} butyric acid methyl ester nanoparticles were prepared on Si substrates and exposed to scCO{sub 2} at different pressures under the isothermal condition of 36 C. The resultant structures could be then preserved by the vitrification process of the glassy polymers via quick pressure quench to atmospheric pressure and subsequently characterized by using various surface sensitive experimental techniques in air. We found that the surface segregation of these nanoparticles is induced in the close vicinity of P = 8.2 MPa where the excess absorption of the fluid into the polymers maximizes. However, when the film thickness becomes less than about 4R{sub g} thick (where R{sub g} is the radius of polymer gyration), the uniform dispersion of the nanoparticles is favorable instead even at the same CO{sub 2} conditions. We clarify that the phase transition is correlated with the emergence of a concentration gradient of the fluid at the polymer/CO{sub 2} interface and is a general phenomenon for different polymer-nanoparticle interactions.

  17. Synthesis of Aromatic Polyhedral Oligomeric Silsesquioxane (POSS) Dianilines for Use in High-Temperature Polyimides

    DTIC Science & Technology

    2012-05-01

    high temperature aromatic polyimides. A general synthetic strategy was devised to improve the structure , yield, and utility of POSS dianilines over... structures in order to delineate the structure -property relationships of POSS and polymer architectures. 15. SUBJECT TERMS POSS, Polyimide...the preparation of high temperature aromatic  polyimides.  A general synthetic strategy was devised to improve the  structure , yield, and utility  of

  18. Charge transfer in photovoltaics consisting of interpenetrating networks of conjugated polymer and TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Arango, A. C.; Carter, S. A.; Brock, P. J.

    1999-03-01

    We study the effect of blended and layered titanium dioxide (TiO2) nanoparticles on charge transfer processes in conjugated polymer photovoltaics. A two order of magnitude increase in photoconductivity and sharp saturation is observed for layered versus blended structures, independent of the cathode work function. Using electrodes with similar work functions, we observe low dark currents and open circuit voltages of 0.7 V when a TiO2 nanoparticle layer is self-assembled onto the indium-tin-oxide electrode. Our results for the layered morphologies are consistent with charge collection by exciton diffusion and dissociation at the TiO2 interface.

  19. Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions

    PubMed Central

    Ledin, Petr A.; Xu, Weinan; Friscourt, Frédéric; Boons, Geert-Jan; Tsukruk, Vladimir V.

    2016-01-01

    Conjugation of small organic molecules and polymers to polyhedral oligosilsesquioxane (POSS) cores results in novel hybrid materials with unique physical characteristics. We report here an approach in which star-shaped organic–inorganic scaffolds bearing eight cyclooctyne moieties can be rapidly functionalized via strain-promoted azide–alkyne cycloaddition (SPAAC) to synthesize a series of nearly monodisperse branched core–shell nanoparticles with hydrophobic POSS cores and hydrophilic arms. We established that SPAAC is a robust method for POSS core octafunctionalization with the reaction rate constant of 1.9 × 10−2 M−1 s−1. Functionalization with poly(ethylene glycol) (PEG) azide, fluorescein azide, and unprotected lactose azide gave conjugates which represent different classes of compounds: polymer conjugates, fluorescent dots, and bioconjugates. These resulting hybrid compounds were preliminarily tested for their ability to self-assemble in solution and at the air–water interface. We observed the formation of robust smooth Langmuir monolayers with diverse morphologies. We found that polar lactose moieties are completely submerged into the subphase whereas the relatively hydrophobic fluorescein arms had extended conformation at the interface, and PEG arms were partially submerged. Finally, we observed the formation of stable micelles with sizes between 70 and 160 nm in aqueous solutions with size and morphology of the structures dependent on the molecular weight and the type of the peripheral hydrophilic moieties. PMID:26131712

  20. Remarkable swelling capability of amino acid based cross-linked polymer networks in organic and aqueous medium.

    PubMed

    Roy, Saswati Ghosh; Haldar, Ujjal; De, Priyadarsi

    2014-03-26

    This work reports design and synthesis of side chain amino acid based cross-linked polymeric gels, able to switch over from organogel to hydrogel by a simple deprotection reaction and showing superabsorbancy in water. Amino acid based methacrylate monomers, tert-butoxycarbonyl (Boc)-l/d-alanine methacryloyloxyethyl ester (Boc-l/d-Ala-HEMA), have been polymerized in the presence of a cross-linker via conventional free radical polymerization (FRP) and the reversible addition-fragmentation chain transfer (RAFT) technique for the synthesis of cross-linked polymer gels. The swelling behaviors of these organogels are investigated in organic solvents, and they behave as superabsorbent materials for organic solvents such as dichloromethane, acetone, tetrahydrofuran, etc. Swollen cross-linked polymer gels release the absorbed organic solvent rapidly. After Boc group deprotection from the pendant alanine moiety, the organogels transform to the hydrogels due to the formation of side chain ammonium (-NH3(+)) groups, and these hydrogels showed a significantly high swelling ratio (∼560 times than their dry volumes) in water. The morphology of organogels and hydrogels is studied by field emission scanning electron microscopy (FE-SEM). Amino acid based cross-linked gels could find applications as absorbents for oil spilled on water as well as superabsorbent hydrogels.

  1. Preparation and wear behavior of polymer matrix composites with an interpenetrating network structure derived from natural sponge.

    PubMed

    Wang, Tianchi; Zhou, Tianle; Xiong, Dangsheng

    2010-03-01

    Natural sponge was used as a template to produce carbon/epoxy resin and (carbon+silicon carbide)/epoxy resin composites with interpenetrating network structures. Carbon with a network structure was first obtained by pyrolysis of the natural sponge. The composites were then obtained by injecting epoxy resin and silicone resin into the carbon. Their microstructures and wear properties were analyzed. The results show that the natural structure of sponge controlled the interpenetrating network structures of the composites. The netlike carbon in the composites reduced the wear rate of the epoxy resin. Compared with the carbon/epoxy resin composite, the (carbon+silicon carbide)/epoxy resin composite shows better wear resistance.

  2. Networks.

    ERIC Educational Resources Information Center

    Maughan, George R.; Petitto, Karen R.; McLaughlin, Don

    2001-01-01

    Describes the connectivity features and options of modern campus communication and information system networks, including signal transmission (wire-based and wireless), signal switching, convergence of networks, and network assessment variables, to enable campus leaders to make sound future-oriented decisions. (EV)

  3. The development of a high-throughput gradient array apparatus for the study of porous polymer networks.

    SciTech Connect

    Majumdar, Partha; Lee, Elizabeth; Chisholm, Bret J.; Dirk, Shawn M.; Weisz, Michael; Bahr, James; Schiele, Kris

    2010-01-01

    A gradient array apparatus was constructed for the study of porous polymers produced using the process of chemically-induced phase separation (CIPS). The apparatus consisted of a 60 element, two-dimensional array in which a temperature gradient was placed in the y-direction and composition was varied in the x-direction. The apparatus allowed for changes in opacity of blends to be monitored as a function of temperature and cure time by taking images of the array with time. The apparatus was validated by dispense a single blend composition into all 60 wells of the array and curing them for 24 hours and doing the experiment in triplicate. Variations in micron scale phase separation were readily observed as a function of both curing time and temperature and there was very good well-to-well consistency as well as trial-to-trial consistency. Poragen of samples varying with respect to cure temperature was removed and SEM images were obtained. The results obtained showed that cure temperature had a dramatic affect on sample morphology, and combining data obtained from visual observations made during the curing process with SEM data can enable a much better understanding of the CIPS process and provide predictive capability through the relatively facile generation of composition-process-morphology relationships. Data quality could be greatly enhanced by making further improvements in the apparatus. The primary improvements contemplated include the use of a more uniform light source, an optical table, and a CCD camera with data analysis software. These improvements would enable quantification of the amount of scattered light generated from individual elements as a function of cure time. In addition to the gradient array development, porous composites were produced by incorporating metal particles into a blend of poragen, epoxy resin, and crosslinker. The variables involved in the experiment were metal particle composition, primary metal particle size, metal concentration

  4. Microgravity Polymers

    NASA Technical Reports Server (NTRS)

    1986-01-01

    A one-day, interactive workshop considering the effects of gravity on polymer materials science was held in Cleveland, Ohio, on May 9, 1985. Selected programmatic and technical issues were reviewed to introduce the field to workshop participants. Parallel discussions were conducted in three disciplinary working groups: polymer chemistry, polymer physics, and polymer engineering. This proceedings presents summaries of the workshop discussions and conclusions.

  5. Oil and fat absorbing polymers

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr. (Inventor)

    1977-01-01

    A method is described for forming a solid network polymer having a minimal amount of crosslinking for use in absorbing fats and oils. The polymer remains solid at a swelling ratio in oil or fat of at least ten and provides an oil absorption greater than 900 weight percent.

  6. Process for controlling morphology and improving thermal mechanical performance of high performance interpenetrating and semiinterpenetrating polymer networks

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H. (Inventor); Hansen, Marion G. (Inventor)

    1998-01-01

    In the process of the present invention, a non-polar, aprotic solvent is removed from an oligomer/polymer solution by freeze-drying in order to produce IPNs and semi-IPNs. By thermally quenching the solution to a solid in a short length of time, the size of the minor constituent-rich regions is greatly reduced as they are excluded along with the major constituent from the regions of crystallizing solvent. The use of this process sequence of controlling phase morphology provides IPNs and semi-IPNs with improved fracture toughness, microcracking resistance, and other physical-mechanical properties as compared to IPNs and semi-IPNs formed when the solvent is evaporated rather than sublimed.

  7. Process for controlling morphology and improving thermal-mechanical performance of high performance interpenetrating and semi-interpenetrating polymer networks

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H. (Inventor); Hansen, Marion G. (Inventor)

    1997-01-01

    In the process of the present invention, a non-polar, aprotic solvent is removed from an oligomer/polymer solution by freeze-drying in order to produce IPNs and semi-IPNs. By thermally quenching the solution to a solid in a short length of time, the size of the minor constituent-rich regions is greatly reduced as they are excluded along with the major constituent from the regions of crystallizing solvent. The use of this process sequence of controlling phase morphology provides IPNs and semi-IPNs with improved fracture toughness, microcracking resistance, and other physical-mechanical properties as compared to IPNs and semi-IPNs formed when the solvent is evaporated rather than sublimed.

  8. Tunable porosity of crosslinked-polyhedral oligomeric silsesquioxane (POSS) supports for palladium-catalyzed aerobic alcohol oxidation in water.

    PubMed

    Sangtrirutnugul, Preeyanuch; Chaiprasert, Thanawat; Hunsiri, Warodom; Jitjaroendee, Thanudkit; Songkhum, Patsaya; Laohhasurayotin, Kritapas; Osotchan, Tanakorn; Ervithayasuporn, Vuthichai

    2017-03-24

    Polyhedral oligomeric silsesquioxane (POSS)-based materials, poly-POSS-Tn [n = 8 (1), 10 (2), 12 (3), and mix (4)], were prepared in high yields via free radical polymerization of corresponding pure forms of methacrylate-functionalized POSS monomers, MMA-POSS-Tn (n = 8, 10, 12), and the mixture form, MMA-POSS-Tmix. Powder X-ray diffraction (XRD) spectra and BET analysis indicate that 1-4 are amorphous materials with high surface areas (683-839 m2•g-1). The surface areas and total pore volumes follow the trend: poly-POSS-T12 > poly-POSS-T10 > poly-POSS-Tmix > poly-POSS-T8. In addition, based on Barrett-Joyner-Halenda (BJH) analysis, poly-POSS-T12 contains the highest amount of mesopores. The Pd nanoparticles immobilized on poly-POSS-Tn [n = 8 (5), 10 (6), 12 (7), and mix (8)] are well dispersed with 4-6 wt% Pd content and similar average particle size of 6.2-6.5 nm, according to transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) and microwave plasma-atomic emission spectroscopy (MP-AES). At 90 oC, the stabilized Pd nanoparticles in 5-8 catalyzed aerobic oxidation of benzyl alcohol to benzaldehyde in 72-100% yields at 6 h using a mixture of a H2O/Pluronic (P123) solution. The PdNp@poly-POSS-T8 catalyst (5) exhibited the lowest catalytic activity, as a result of its lowest surface areas, total pore volumes, and amounts of mesopores. With the catalyst 8, various benzyl alcohol derivatives were converted to the corresponding aldehydes in good to excellent yields. However, with alcoholic substrates featuring electron-withdrawing substituents, high conversions were achieved with one equivalent of K2CO3 additive and longer reaction times.

  9. Functionalized bridged silsesquioxane-based nanostructured microspheres: performance as novel drug-delivery devices in bone tissue-related applications.

    PubMed

    Romeo, Hernán Esteban; Fanovich, María Alejandra

    2012-05-01

    Two kinds of functionalized nanostructured hybrid microspheres, based on the bridged silsesquioxane family, were synthesized by employing the sol-gel method via self-assembly of two different organic-inorganic bridged monomers. The architecture reached at molecular level allowed the incorporation of acetylsalicylic acid (ASA) as an anti-inflammatory model drug. The ASA-functionalized microspheres were characterized as delivery devices in simulated body fluid (SBF). The release behaviors of the synthesized microspheres (Fickian or anomalous diffusion mechanisms) were shown to be dependent on the chemical nature of the bridged monomers employed to synthesize the hybrid materials. The functionalized microspheres were proposed as delivery systems into calcium phosphate cements (CPCs), in order to slow down the characteristic drug-delivery kinetics of this kind of bone tissue-related materials. The incorporation of the new functionalized microparticles into the CPCs represented a viable methodology to modify the ASA-release kinetics in comparison to a conventional CPC containing the drug dispersed into the solid phase. The ASA-delivery profiles obtained from the microsphere-loaded CPCs showed that 40-60% of drug can be released after 2 weeks of testing in SBF. The inclusion of the microspheres into the CPC matrices allowed modification of the release profiles through a mechanism that involved two stages: (1) the diffusion of the drug through the organic-inorganic matrix of the microspheres (according to a Fickian or anomalous diffusion, depending on the nanostructuring) and (2) the subsequent diffusion of the drug through the ceramic matrix of the hardened cements. The release behavior of the composite cements was shown to be dependent on the nanostructuring of the hybrid microspheres, which can be selectively tailored by choosing the desired chemical structure of the bridged precursors employed in the sol-gel synthesis. The obtained results demonstrated the ability of

  10. A one-step method for the synthesis of a vinyl-containing silsesquioxane and other organolithic macromolecular precursors

    SciTech Connect

    Yuchs, S.E.; Carrado, K.A.

    1996-01-03

    Octasilsesquioxanes are well-known molecules that are presently being used as molecular building blocks in the synthesis of ceramic materials. These materials are synthesized by a variety of means, including mixing several different solution species, photochlorination of [Si{sub 8}O{sub 12}]H{sub 8} followed by treatment with neat methyl cyanide, use of acetic acid and trimethoxy-silane saturated with anhydrous HCl, and employment of excess reactants and long time scales (1-3 years). These methods were inconvenient because they were multistep procedures that used high quantities of starting materials and long reaction times, and delivered low yields of the desired products. Recently, Moran et al. reported a simple method for the synthesis of octakis(dimethylsiloxyl)octasilsesquioxane, [Si{sub 8}O{sub 12}](OSi(CH{sub 3}){sub 2}H){sub 8}. Their method involves the treatment of tetramethylammonium silicate with chlorodimethylsesquioxane in a mixed organic solvent. A one-step synthesis for the introduction of a vinyl functional group onto an octasilsesquioxane molecule has now been developed using the method of Moran. The target molecule, Octakis(vinyldimethylsiloxyl)octasilsesquioxane, [Si{sub 8}O{sub 12}](OSi-(CH{sub 3}){sub 2}(CHCH{sub 2})){sub 8}, is synthesized in high yields using tetramethylammonium silicate and chlorodimethylvinylsilane. The target molecule and several new derivatives have been synthesized and characterized by high-resolution {sup 1}H, {sup 13}C, and {sup 29}Si NMR and by IR. This method is more practical than previous synthesis schemes for the preparation of the vinyl derivative. This new synthesis route allows for the rapid formation of an air-stable silsesquioxane molecule that is easily derivatized to form new organolithic macromolecular materials (OMM`s).

  11. Ferrocene adsorbed into the porous octakis(hydridodimethylsiloxy)silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination

    SciTech Connect

    Ribeiro do Carmo, Devaney; Lataro Paim, Leonardo; Ramos Stradiotto, Nelson

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Octakis(hydridodimethylsiloxi)silsesquioxane was synthesized and Ferrocene was adsorbed. Black-Right-Pointing-Pointer Polymeric net through electrostatic interactions was observed. Black-Right-Pointing-Pointer The novel materials presents electroacatalytic activity for Ascorbic acid. -- Abstract: Octakis(hydridodimethylsiloxi)silsesquioxane (Q{sub 8}M{sub 8}{sup H}) was synthesized and Ferrocene was adsorbed in a polymeric net through electrostatic interactions, with anion forming after the cleavage of any siloxy groups (ESFc). The nanostructured materials (Q{sub 8}M{sub 8}{sup H} and EsFc) were characterized by Fourier transform infrared spectra (FT-IR), nuclear magnetic resonance (NMR), X-ray diffraction (XRD), Thermogravimetric analyses and Voltammetric technique The cyclic voltammograms of the graphite paste electrode modified with ESFc showed one redox couple with E{sup 0} Prime = 0.320 V (1.0 mol L{sup -1} NaCl, v = 50 mV s{sup -1}), with a diffusion-controlled process and the redox process shows electrocatalytic activity for the oxidation of ascorbic acid.

  12. IUPAC International Symposium on Polymers for Advanced Technologies, Jerusalem, Israel, Aug. 16-21, 1987, Proceedings

    SciTech Connect

    Lewin, M.

    1988-01-01

    The present conference discusses topics in radiation-sensitive, radiation-modified, and cured polymers, polymers of photoconductive, electroconductive, and piezoelectric type, polymers for advanced structures, liquid-crystal polymers, high-performance polymers compounded from flexible macromolecules, polymer networks, polymer blends, and the matching of composites with adhesives. Attention is given to the industrial radiation-curing of polymers, a frequency-analysis of ferroelectricity, liquid crystal polyester fibers, photochromic and thermochromic liquid crystals, diacetylene-based single-crystal fibers, interpenetrating polymer networks, chain-length development in complex epoxy-amine matrices, and a statistical-thermodynamic theory of polymer precipitation fractionation.

  13. Highly enhanced dynamics of microdomains ordering by solvent vapor annealing of thin block copolymer films on polymer network supports

    NASA Astrophysics Data System (ADS)

    Tsarkova, Larisa; Stenbock-Fermor, Anja; Böker, Alexander; Knoll, Armin; IBM Reserach Collaboration; DWI Team

    2014-03-01

    We studied the solvent driven ordering dynamics of block copolymer films supported by a densely cross-linked organic hard mask (HM) designed for lithographic fabrication. We found that the ordering of microphase separated domains on the HM layer proceeds significantly faster as compared to similar films on silicon wafers. This leads to a pronounced enhancement of the dynamics of both the terrace-formation as well as the long-range lateral ordering of the microdomains. The effect is independent on the chemical structure and volume composition of the studied block copolymers (cylinder-/ lamella-forming). Importantly, enhanced ordering is achieved even at a reduced degree of swelling corresponding to an intermediate to strong segregation regime, when similar films on conventional substrate show very limited ordering. In-situ ellipsometric measurements of the swollen films revealed an insignificant increase by 1-3 vol. % in the solvent up-take by HM-supported films. Therefore we attribute the enhanced dynamics to reduced interactions at the block copolymer/HM-support interface. Apart from immediate technological impact in block copolymer-assisted nanolithography, our findings convey novel insight into effects of molecular architecture on polymer-solvent interactions. Forckenbeckstr. 50 52056 Aachen, Germany.

  14. Glass-like dynamics of the strain-induced coil/helix transition on a permanent polymer network

    NASA Astrophysics Data System (ADS)

    Ronsin, O.; Caroli, C.; Baumberger, T.

    2016-02-01

    We study the stress response to a step strain of covalently bonded gelatin gels in the temperature range where triple helix reversible crosslink formation is prohibited. We observe slow stress relaxation towards a T-dependent finite asymptotic level. We show that this is assignable to the strain-induced coil → helix transition, previously evidenced by Courty et al. [Proc. Natl. Acad. Sci. U. S. A. 102, 13457 (2005)], of a fraction of the polymer strands. Relaxation proceeds, in a first stage, according to a stretched exponential dynamics, then crosses over to a terminal simple exponential decay. The respective characteristic times τK and τf exhibit an Arrhenius-like T-dependence with an associated energy E incompatibly larger than the activation barrier height for the isomerisation process which sets the clock for an elementary coil → helix transformation event. We tentatively assign this glass-like slowing down of the dynamics to the long-range couplings due to the mechanical noise generated by the local elementary events in this random elastic medium.

  15. Polymer-facilitated low temperature fusing of spray-coated silver nanowire networks as transparent top and bottom electrodes in small molecule organic photovoltaics (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Selzer, Franz; Weiß, Nelli; Kneppe, David; Bormann, Ludwig; Sachse, Christoph; Gaponik, Nikolai; Eychmüller, Alexander; Leo, Karl; Müller-Meskamp, Lars

    2015-10-01

    Networks of silver nanowires (AgNWs) are promising candidates for transparent conducting electrodes in organic photovoltaics (OPV), as they achieve similar performance as the commonly used indium tin oxide (ITO) at lower cost and increased flexibility. The initial sheet resistance (Rs) of AgNW electrodes typically needs to be reduced by a post-annealing step (90 min@200 °C), being detrimental for processing on polymeric substrates. We present novel low temperature-based methods to integrate AgNWs in organic small molecule-based photovoltaics, either as transparent and highly conductive bottom-electrode or, for the first time, as spray-coated AgNW top-electrode. The bottom-electrodes are prepared by organic matrix assisted low-temperature fusing. Here, selected polymers are coated below the AgNWs to increase the interaction between NWs and substrate. In comparison to networks without these polymeric sublayers, the Rs is reduced by two orders of magnitude. AgNW top-electrodes are realized by dispersing modified high-quality AgNWs in inert solvents, which do not damage small molecule layers. Accordingly, our AgNW dispersion can be spray-coated onto all kind of OPV devices. Both bottom- and top-electrodes show a Rs of <11 Ω/ at >87 % transparency directly after spray-coating at very low substrate temperatures of <80 °C. We also demonstrate the implementation of our AgNW electrodes in organic solar cells. The corresponding devices show almost identical performance compared to organic solar cells exploiting ITO as bottom or thermally evaporated thin-metal as top-electrode.

  16. Networking.

    ERIC Educational Resources Information Center

    Duvall, Betty

    Networking is an information giving and receiving system, a support system, and a means whereby women can get ahead in careers--either in new jobs or in current positions. Networking information can create many opportunities: women can talk about how other women handle situations and tasks, and previously established contacts can be used in…

  17. Damping, thermal, and mechanical properties of polyurethane based on poly(tetramethylene glycol)/epoxy interpenetrating polymer networks: effects of composition and isocyanate index

    NASA Astrophysics Data System (ADS)

    Wang, Qihua; Chen, Shoubing; Wang, Tingmei; Zhang, Xinrui

    2011-07-01

    A series of polyurethane (PU) samples based on poly(tetramethylene glycol)/epoxy resin (EP) graft interpenetrating polymer networks (IPNs) were prepared and their damping, thermal, and mechanical properties were systematically studied in terms of composition and the value of the PU isocyanate index ( R). The damping properties and thermal stability measurements revealed that the formation of PU/EP IPN could improve not only the damping capacity but also the thermal stability. Meanwhile, mechanical tests showed that the tensile strengths of the IPNs decreased while their impact strengths increased with increasing PU content. The value of R also had significant impacts on the properties of the IPNs when the PU and EP ratio was fixed, which could be an effective means for manipulating the fabrication of PU/EP IPNs. The morphologies of the PU/EP IPNs were observed by SEM and AFM characterization and the relationship between the morphologies and properties is discussed. With the results in hand, the PU/EP IPNs hold promise for use in structural damping materials.

  18. Nanoscale control of the network morphology of high efficiency polymer fullerene solar cells by the use of high material concentration in the liquid phase.

    PubMed

    Radbeh, R; Parbaile, E; Bouclé, J; Di Bin, C; Moliton, A; Coudert, V; Rossignol, F; Ratier, B

    2010-01-22

    Despite the constant improvement of their power conversion efficiencies, organic solar cells based on an interpenetrating network of a conjugated polymer as donor and fullerene derivatives as acceptor materials still need to be improved for commercial use. In this context, we present a study on the optimization of solar cells based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) by varying a specific cell parameter, namely the concentration of the active layer components in the liquid phase before blend film deposition, in order to improve device performance and to better understand the relation between morphology and device operation. Our study shows a significant increase of the short-circuit current, open-circuit voltage and cell efficiency by properly choosing the formulation of the initial blend before film deposition. We demonstrate that the active layer morphology, which is strongly dependent on the initial material concentrations and the processing conditions, can greatly impact the electronic characteristics of the device, especially regarding charge recombination dynamics at the donor-acceptor interface. Our optimized P3HT:PCBM device exhibits both slow recombination and high photocurrent generation associated with an overall power conversion efficiency of 4.25% under 100 mW cm(-2) illumination (AM1.5G).

  19. A technique for real-time detection, location and quantification of damage in large polymer composite structures made of electrically non-conductive fibers and carbon nanotube networks

    NASA Astrophysics Data System (ADS)

    Naghashpour, Ali; Van Hoa, Suong

    2013-11-01

    In this work, we have developed a novel, practical and real-time structural health monitoring (SHM) technique to detect, locate and quantify damage that occurs at one or more locations in large polymer composite structures (LPCSs) made of electrically non-conductive fibers and carbon nanotube networks. Our technique exploits the piezoresistive effect of multiwalled carbon nanotubes (MWCNTs) in epoxy resin. The electrically conductive epoxy resin was used to prepare glass fiber reinforced composite plates. The plates were marked with grid points where electrically conductive silver-epoxy pastes were deposited. The electrical resistances between the grid points were measured and used as a reference set. Two new concepts are introduced. One is uniformity of MWCNT distribution which gives rise to uniformity in electrical conductivity. The second is maximum sensitivity to change in electrical resistance due to the occurrence of damage. These issues are demonstrated as criteria to determine the optimal quantity of MWCNTs. This optimal quantity is used to assure damage detectability at any region in the large plates. Drilled holes and impact testing were conducted to simulate damage. The damage causes the electrical resistance between the contact points surrounding the damage to increase. This increase is used to detect, locate and quantify damage.

  20. Peri-implant bone formation and implant integration strength of peptide-modified p(AAM-co-EG/AAC) interpenetrating polymer network-coated titanium implants.

    PubMed

    Barber, Thomas A; Ho, James E; De Ranieri, Aladino; Virdi, Amarjit S; Sumner, Dale R; Healy, Kevin E

    2007-02-01

    Interpenetrating polymer networks (IPNs) of poly (acrylamide-co-ethylene glycol/acrylic acid) functionalized with an -Arg-Gly-Asp- (RGD) containing 15 amino acid peptides, derived from rat bone sialoprotein (bsp-RGD(15), were grafted to titanium implants in an effort to modulate bone formation in the peri-implant region in the rat femoral ablation model. Bone-implant contact (BIC) and bone formation within the medullary canal were determined using microcomputed tomography at 2 and 4 weeks postimplantation. BIC for bsp-RGD(15)-IPN implants was enhanced relative to hydroxyapatite tricalcium phosphate (HA-TCP) coated implants, but was similar to all other groups. Aggregate bone formation neither indicated a dose-dependent effect of bsp-RGD(15) nor a meaningful trend. Mechanical testing of implant fixation revealed that only the HA-TCP coated implants supported significant (>1 MPa) interfacial shear strength, despite exhibiting lower overall BIC, an indication that bone ingrowth into the rougher coating was the primary mode of implant fixation. While no evidence was found to support the hypothesis that bsp-RGD(15)-modified IPN coated implants significantly impacted bone-implant bonding, these results point to the lack of correlation between in vitro studies employing primary osteoblasts and in vivo wound healing in the peri-implant region.

  1. Stretchable and strong cellulose nanopaper structures based on polymer-coated nanofiber networks: an alternative to nonwoven porous membranes from electrospinning.

    PubMed

    Sehaqui, Houssine; Morimune, Seira; Nishino, Takashi; Berglund, Lars A

    2012-11-12

    Nonwoven membranes based on electrospun fibers are of great interest in applications such as biomedical, filtering, and protective clothing. The poor mechanical performance is a limitation, as is some of the electrospinning solvents. To address these problems, porous nonwoven membranes based on nanofibrillated cellulose (NFC) modified by a hydroxyethyl cellulose (HEC) polymer coating are prepared. NFC/HEC aqueous suspensions are subjected to simple vacuum filtration in a paper-making fashion, followed by supercritical CO(2) drying. These nonwoven nanocomposite membranes are truly nanostructured and exhibit a nanoporous network structure with high specific surface area, as analyzed by nitrogen adsorption and FE-SEM. Mechanical properties evaluated by tensile tests show high strength combined with remarkably high strain to failure of up to 55%. XRD analysis revealed significant fibril realignment during tensile stretching. After postdrawing of the random mats, the modulus and strength are strongly increased. The present preparation route uses components from renewable resources, is environmentally friendly, and results in permeable membranes of exceptional mechanical performance.

  2. Interpenetrating polymer networks containing gelatin modified with PEGylated RGD and soluble KGF: synthesis, characterization, and application in in vivo critical dermal wound.

    PubMed

    Waldeck, Heather; Chung, Amy S; Kao, Weiyuan John

    2007-09-15

    The purpose of this study was to evaluate the biocompatibility and the efficacy in wound healing of a gelatin-based interpenetrating polymer network (IPN) containing poly(ethylene glycol) (PEG)-ylated RGD and soluble KGF-1 (RGD-IPN+KGF). IPNs were applied to full-thickness wounds on a rat model. Wound healing was assessed through histological grading of the host response and percent area contraction at 2 days, 1 week, 2 weeks, and 3 weeks. A control IPN containing unmodified gelatin (unmod-IPN) and a conventional clinical bandage were applied to similar wounds and also evaluated. During the first week of healing, the unmod-IPN and conventional dressing wound showed a greater amount of contraction than that of RGD-IPN+KGF. However, by 3 weeks the extent of wound contraction was comparable between treatments. The RGD-IPN+KGF treated wound demonstrated lower macrophage and fibroblast densities at 3 weeks as compared to unmod-IPN treated wounds. RGD-IPN+KGF acted as a tissue scaffold while preventing the entry of foreign bodies, advantages not seen with the conventional dressing. The extent of cellularity and extracellular matrix organization was higher for wounds healed with RGD-IPN+KGF than those healed with unmod-IPN. These results indicate that both soluble and immobilized bioactive factors can be incorporated into our IPN platform to enhance the rate and the quality of dermal wound healing.

  3. Polyvinylpyrrolidone-based semi-interpenetrating polymer networks as highly selective and chemically stable membranes for all vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

    2016-09-01

    Vanadium redox flow batteries (VRFBs) with their high flexibility in configuration and operation, as well as long cycle life are competent for the requirement of future energy storage systems. Nevertheless, due to the application of perfluorinated membranes, VRFBs are plagued by not only the severe migration issue of vanadium ions, but also their high cost. Herein, we fabricate semi-interpenetrating polymer networks (SIPNs), consisting of cross-linked polyvinylpyrrolidone (PVP) and polysulfone (PSF), as alternative membranes for VRFBs. It is demonstrated that the PVP-based SIPNs exhibit extremely low vanadium permeabilities, which contribute to the well-established hydrophilic/hydrophobic microstructures and the Donnan exclusion effect. As a result, the coulombic efficiencies of VRFBs with PVP-based SIPNs reach almost 100% at 40 mA cm-2 to 100 mA cm-2; the energy efficiencies are more than 3% higher than those of VRFBs with Nafion 212. More importantly, the PVP-based SIPNs exhibit a superior chemical stability, as demonstrated both by an ex situ immersion test and continuously cycling test. Hence, all the characterizations and performance tests reported here suggest that PVP-based SIPNs are a promising alternative membrane for redox flow batteries to achieve superior cell performance and excellent cycling stability at the fraction of the cost of perfluorinated membranes.

  4. Modeling out-of-plane actuation in thin-film nematic polymer networks: From chiral ribbons to auto-origami boxes via twist and topology

    PubMed Central

    Gimenez-Pinto, Vianney; Ye, Fangfu; Mbanga, Badel; Selinger, Jonathan V.; Selinger, Robin L. B.

    2017-01-01

    Various experimental and theoretical studies demonstrate that complex stimulus-responsive out-of-plane distortions such as twist of different chirality, emergence of cones, simple and anticlastic bending can be engineered and pre-programmed in a liquid crystalline rubbery material given a well-controlled director microstructure. Via 3-d finite element simulation studies, we demonstrate director-encoded chiral shape actuation in thin-film nematic polymer networks under external stimulus. Furthermore, we design two complex director fields with twisted nematic domains and nematic disclinations that encode a pattern of folds for an auto-origami box. This actuator will be flat at a reference nematic state and form four well-controlled bend distortions as orientational order changes. Device fabrication is applicable via current experimental techniques. These results are in qualitative agreement with theoretical predictions, provide insight into experimental observations, and demonstrate the value of finite element methods at the continuum level for designing and engineering liquid crystal polymeric devices. PMID:28349949

  5. Novel composite membrane coated with a poly(diallyldimethylammonium chloride)/urushi semi-interpenetrating polymer network for non-aqueous redox flow battery application

    NASA Astrophysics Data System (ADS)

    Cho, Eunhae; Won, Jongok

    2016-12-01

    Novel composite membranes of a semi-interpenetrating network (semi-IPN) coated on the surfaces of a porous Celgard 2400 support are prepared and investigate for application in a non-aqueous redox flow battery (RFB). A natural polymer, urushi, is used for the matrix because of its high mechanical robustness, and poly(diallyldimethylammonium chloride) (PDDA) provides anionic exchange sites. The PDDA/urushi (P/U) semi-IPN film is prepared by the photo polymerization of urushiol in the presence of PDDA. The thin layer composed of the P/U semi-IPN on the porous support provides selectivity while maintaining the ion conductivity. The coulombic and energy efficiencies increase with increasing amounts of PDDA in the P/U semi-IPN layer, and the values reach 69.5% and 42.5%, respectively, for the one containing 40 wt% of PDDA. These values are substantially higher than those of the Neosepta AHA membrane and the Celgard membrane, indicating that the selective layer reduces the crossover of the redox active species through the membrane. This result implies that the formation of composite membranes using semi-IPN selective layers on the dimensionally stable porous membrane enable the successful use of a non-aqueous RFB for future energy storage systems.

  6. Two-step build-up of a thermoreversible polymer network: From early local to late collective dynamics

    NASA Astrophysics Data System (ADS)

    Souguir, H.; Ronsin, O.; Caroli, C.; Baumberger, T.

    2015-04-01

    We probe the mechanisms at work in the build-up of thermoreversible gel networks, with the help of hybrid gelatin gels containing a controlled density of irreversible, covalent crosslinks (CLs), which we quench below the physical gelation temperature. The detailed analysis of the dependence on covalent crosslink density of both the shear modulus and optical activity evolutions with time after quench enables us to identify two stages of the physical gelation process, separated by a temperature-dependent crossover modulus: (i) an early nucleation regime during which rearrangements of the triple-helix CLs play a negligible role, and (ii) a late, logarithmic aging one, which is preserved, though slowed down, in the presence of irreversible CLs. We show that aging is fully controlled by rearrangements and discuss the implication of our results in terms of the switch from an early, local dynamics to a late, cooperative long-range one.

  7. Two-step build-up of a thermoreversible polymer network: From early local to late collective dynamics.

    PubMed

    Souguir, H; Ronsin, O; Caroli, C; Baumberger, T

    2015-04-01

    We probe the mechanisms at work in the build-up of thermoreversible gel networks, with the help of hybrid gelatin gels containing a controlled density of irreversible, covalent crosslinks (CLs), which we quench below the physical gelation temperature. The detailed analysis of the dependence on covalent crosslink density of both the shear modulus and optical activity evolutions with time after quench enables us to identify two stages of the physical gelation process, separated by a temperature-dependent crossover modulus: (i) an early nucleation regime during which rearrangements of the triple-helix CLs play a negligible role, and (ii) a late, logarithmic aging one, which is preserved, though slowed down, in the presence of irreversible CLs. We show that aging is fully controlled by rearrangements and discuss the implication of our results in terms of the switch from an early, local dynamics to a late, cooperative long-range one.

  8. Piezoelectric Polymers

    NASA Technical Reports Server (NTRS)

    Harrison, J. S.; Ounaies, Z.; Bushnell, Dennis M. (Technical Monitor)

    2001-01-01

    The purpose of this review is to detail the current theoretical understanding of the origin of piezoelectric and ferroelectric phenomena in polymers; to present the state-of-the-art in piezoelectric polymers and emerging material systems that exhibit promising properties; and to discuss key characterization methods, fundamental modeling approaches, and applications of piezoelectric polymers. Piezoelectric polymers have been known to exist for more than forty years, but in recent years they have gained notoriety as a valuable class of smart materials.

  9. Polymer infiltration studies

    NASA Technical Reports Server (NTRS)

    Marchello, Joseph M.

    1991-01-01

    Progress was made on the preparation of carbon fiber composites using advanced polymer resins. Processes reported include powder towpreg process, weaving towpreg made from dry powder prepreg, composite from powder coated towpreg, and toughening of polyimide resin (PMR) composites by semi-interpenetrating networks. Several important areas of polymer infiltration into fiber bundles will be researched. Preparation to towpreg for textile preform weaving and braiding and for automated tow placement is a major goal, as are the continued development of prepregging technology and the various aspects of composite part fabrication.

  10. Nanofabrication of super-high-aspect-ratio structures in hydrogen silsesquioxane from direct-write e-beam lithography and hot development.

    SciTech Connect

    Ocola, L. E.; Tirumala, V. R.; Center for Nanoscale Materials; NIST

    2008-11-01

    Super-high-aspect-ratio structures (>10) in hydrogen silsesquioxane resist using direct write electron beam lithography at 100 kV and hot development and rinse are reported. Posts of 100 nm in width and 1.2 {micro}m tall have been successfully fabricated without the need of supercritical drying. Hot rinse solution with isopropyl alcohol has been used to reduce surface tension effects during drying. Dose absorption effects have been observed and modeled using known Monte Carlo models. These results indicate that for e-beam exposures of thick negative resists (>1 {micro}m), the bottom of the structures will have less cross-link density and therefore will be less stiff than the top. These results will have impact in the design of high-aspect-ratio structures that can be used in microelectromechanical system devices and high-aspect-ratio Fresnel zone plates.

  11. Modeling and fabrication of lithium polymer ion batteries designed for wireless sensor network applications and printed directly on device

    NASA Astrophysics Data System (ADS)

    Steingart, Daniel Artemis

    CVD produce excellent thin film microstructures, but face considerable problems with regard to stress build up as thickness grows beyond 10 mum. When total battery area is constrained to 1 cm2 a single electrode thickness of 10 mum is simply insufficient to create a useful battery. The second major issue is processing temperature. The processes that are used to deposit most thin film battery materials require temperatures greater than 300°C [3], which is greater than the temperature most CMOS devices can withstand. While electrical engineers may get around this by (1) using a separate chip for the battery or (2) use the battery as the substrate to build the device both cases would require more packaging to protect the batteries, to some degree defeating the purpose of reducing the packaging. To overcome this obstacle, a new method to place the materials necessary to make a battery on a chip has been developed. This process was done at room temperature, at packaging to protect the batteries, to some degree defeating the purpose of reducing the packaging. To overcome this obstacle, a new method to place the materials necessary to make a battery on a chip has been developed. This process is done at room temperature, at atmospheric pressure, and with thicknesses great enough to provide significantly more capacity than thin film solutions. The method uses tools used to apply adhesives, traditionally, including screen-printing and pneumatic extrusion. These methods produce structures that in theory should provide the energy and power density available in large-scale batteries (a feat heretofore not replicated by thin film fabrication methods) and with improvements in solid polymer electrolytes, may provide the necessary power density. These tools can be used to produce capacitors as well, which can help in load leveling the battery, thereby increasing both discharge time and cycle life. Finally, in the course of this research conventional battery test equipment was either

  12. Statistical optimization and artificial neural network modeling for acridine orange dye degradation using in-situ synthesized polymer capped ZnO nanoparticles.

    PubMed

    Dhiman, Nitesh; Markandeya; Singh, Amrita; Verma, Neeraj K; Ajaria, Nidhi; Patnaik, Satyakam

    2017-05-01

    ZnO NPs were synthesized by a prudent green chemistry approach in presence of polyacrylamide grafted guar gum polymer (pAAm-g-GG) to ensure uniform morphology, and functionality and appraised for their ability to degrade photocatalytically Acridine Orange (AO) dye. These ZnO@pAAm-g-GG NPs were thoroughly characterized by various spectroscopic, XRD and electron microscopic techniques. The relative quantity of ZnO NPs in polymeric matrix has been estimated by spectro-analytical procedure; AAS and TGA analysis. The impact of process parameters viz. NP's dose, contact time and AO dye concentration on percentage photocatalytic degradation of AO dyes were evaluated using multivariate optimizing tools, Response Surface Methodology (RSM) involving Box-Behnken Design (BBD) and Artificial Neural Network (ANN). Congruity of the BBD statistical model was implied by R(2) value 0.9786 and F-value 35.48. At RSM predicted optimal condition viz. ZnO@pAAm-g-GG NP's dose of 0.2g/L, contact time of 210min and AO dye concentration 10mg/L, a maximum of 98% dye degradation was obtained. ANOVA indicated appropriateness of the model for dye degradation owing to "Prob.>F" less than 0.05 for variable parameters. We further, employed three layers feed forward ANN model for validating the BBD process parameters and suitability of our chosen model. The evaluation of Levenberg-Marquardt algorithm (ANN1) and Gradient Descent with adaptive learning rate (ANN2) model employed to scrutinize the best method and found experimental values of AO dye degradation were in close to those with predicated value of ANN 2 modeling with minimum error.

  13. Mn4 single-molecule-magnet-based polymers of a one-dimensional helical chain and a three-dimensional network: syntheses, crystal structures, and magnetic properties.

    PubMed

    Tsai, Hui-Lien; Yang, Chen-I; Wernsdorfer, Wolfgang; Huang, Siang-Hua; Jhan, Siang-Yu; Liu, Ming-Hsuan; Lee, Gene-Hsiang

    2012-12-17

    Two Mn(4) single-molecule-magnet (SMM)-based coordination polymers, {[Mn(4)O(salox)(3)(N(3))(3)(DMF)(2)(H(2)O)(dpp)]·0.5MeOH}(n) (1·0.5MeOH; H(2)salox = salicylaldoxime; dpp = 1,3-di-4-pyridylpropane; DMF = N,N-dimethylformamide) and {[Mn(4)O(Me-salox)(3)(N(3))(3)(dpp)(1.5)]·1.5Et(2)O}(n) (2·1.5Et(2)O; Me-H(2)salox = hydroxyphenylethanone oxime), are self-assembled from Mn(ClO(4))(2)·6H(2)O/H(2)salox and Mn(ClO(4))(2)·6H(2)O/Me-H(2)salox systems with dpp and NaN(3) in DMF/MeOH, respectively. Both compounds comprise a mixed-valence tetranuclear manganese core, [Mn(II)Mn(III)(3)O](9+), which serves as a building unit for subsequent assembly via oximate and azido ligands. The flexible dpp ligand links with a Mn(4) unit, leading to the formation of a one-dimensional helical structure in 1·0.5MeOH and a three-dimensional pcu network in 2·1.5Et(2)O. The magnetic data analysis shows that antiferromagnetic interactions within the Mn(4) units resulted in S = (3)/(2) and (7)/(2) ground states for 1·0.5MeOH and 2·1.5Et(2)O, respectively. Both compounds show SMM behavior, as evidenced by frequency-dependent out-of-phase signals in alternating-current magnetic susceptibility and magnetic hysteresis loop studies with an energy barrier of U(eff) = 37 K for 2·1.5Et(2)O.

  14. Effects of different surface finishing procedures on the change in surface roughness and color of a polymer infiltrated ceramic network material

    PubMed Central

    Arslan, Merve; Türker, Nurullah; Barutcigil, Kubilay

    2016-01-01

    PURPOSE Polymer infiltrated ceramic network (PICN) materials, also called hybrid ceramics, are new materials in dental market. The manufacturer of the PICN material VITA Enamic suggests 3 different finishing procedures for this new material. In the present study, surface roughness and color differences caused from different finishing procedures of VITA Enamic were investigated. MATERIALS AND METHODS 120 specimens were prepared in dimensions 2 × 10 × 12 mm from VITA Enamic hybrid ceramic blocks with 'high translucency' and 'translucency 2M2' shades. The specimens were divided into 8 groups. For each group, different finishing procedures suggested by the manufacturer were performed. Surface roughness values were determined by a tactile portable profilometer. Color changes were evaluated using a clinical spectrophotometer. The data were analyzed using one-way ANOVA and Tukey's post-hoc comparison. The significance level was set at α=0.05. RESULTS The roughest surfaces were observed in Glaze Groups. Their surface roughness values were similar to that of the control group. Clinical Kit and Technical Kit groups did not show a statistically significant difference regarding surface roughness (P>.05). The largest color difference regarding ΔE00 was observed in Clinical Kit finishing groups. There were also statistically significant color changes between the groups (P<.05). However, all the groups showed clinically acceptable color change (ΔE00<2.25) except Clinical Kit Groups (ΔE00>2.25). CONCLUSION Within the limitations of the present study, it may be suggested that finishing the VITA Enamic restorations by Technical Kit instead of Glaze and Clinical Kit gives better clinical performance in regard to surface roughness and shade matching. PMID:26949483

  15. Controlled release of clot-dissolving tissue-type plasminogen activator from a poly(L-glutamic acid) semi-interpenetrating polymer network hydrogel.

    PubMed

    Park, Y; Liang, J; Yang, Z; Yang, V C

    2001-07-10

    With the aim of developing an effective therapeutic modality for treatment of thrombosis, a tissue-type plasminogen activator (t-PA)-loaded porous poly(L-glutamic acid) (PLGA) semi-interpenetrating polymer network (semi-IPN) hydrogel was developed as a possible local drug delivery system. Porous structure of hydrogel was essential in this system to yield a large surface area so that t-PA release could be facilitated. This semi-IPN hydrogel was prepared using the method of free-radical polymerization and crosslinking of polyethylene glycol (PEG)-methacrylate through the PLGA network. Sodium bicarbonate (NaHCO(3)) was added to function as a foaming agent under acidic conditions, rendering the semi-IPN hydrogel to be porous. While the added NaHCO(3) provided gas foam in the reaction mixture, the pH in the hydrogel increased to about 7 to 8, which stimulated the polymerization. The porous structure that was presented at both the surface and sublayer was stabilized during hydrogel formation and freeze-drying. The hydrogel thus prepared possessed a porous structure of 10-20 microm in diameter, as determined by scanning electron microscopy. Results showed that the above hydrogel preparation process did not significantly alter the specific activity of the entrapped t-PA with regard to plasminogen activation and fibrin clot lysis ability. The t-PA release from this semi-IPN hydrogel was examined by measuring the plasmin activity using the chromogenic substrate S-2251. Findings in this paper demonstrated that the porous structure of the hydrogel facilitated t-PA release when compared to the dense structure. Aside from the porous structure, other factors including the content of the crosslinker, PLGA and t-PA could all be varied to regulate t-PA release from the hydrogel. These results suggest that a porous PLGA semi-IPN hydrogel could potentially be a useful local delivery system to release active t-PA primarily at the site of a thrombus.

  16. Star Polymers.

    PubMed

    Ren, Jing M; McKenzie, Thomas G; Fu, Qiang; Wong, Edgar H H; Xu, Jiangtao; An, Zesheng; Shanmugam, Sivaprakash; Davis, Thomas P; Boyer, Cyrille; Qiao, Greg G

    2016-06-22

    Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

  17. Polymer Chemistry

    NASA Technical Reports Server (NTRS)

    Williams, Martha; Roberson, Luke; Caraccio, Anne

    2010-01-01

    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  18. Polymers & People

    ERIC Educational Resources Information Center

    Lentz, Linda; Robinson, Thomas; Martin, Elizabeth; Miller, Mary; Ashburn, Norma

    2004-01-01

    Each Tuesday during the fall of 2002, teams of high school students from three South Carolina counties conducted a four-hour polymer institute for their peers. In less than two months, over 300 students visited the Charleston County Public Library in Charleston, South Carolina, to explore DNA, nylon, rubber, gluep, and other polymers. Teams of…

  19. Covalent Percolation and Gold Templating of Carbon NanoTubes Network in Polymer Nanocomposites for Novel Mechanical, Electrical, and Optical Properties. Taiwain - US AFOSR Nanoscience Initiative

    DTIC Science & Technology

    2008-03-26

    stress for craze widening, but also the craze initiation stress. Eventually, few crazes can be drawn to absorb the deformation, and cracking becomes the...stretching. Crazes are crack -like defect that are load-bearing and fibrillated in zone. It thickness by drawing more polymer in from the edge of...Previous works on CNTs as fillers in polymers have been focused primarily on the low-strain elastic behavior and cracking properties [4-13]. Little

  20. Synthetic biodegradable polymers for orthopaedic applications.

    PubMed

    Behravesh, E; Yasko, A W; Engel, P S; Mikos, A G

    1999-10-01

    Synthetic biodegradable polymers offer an alternative to the use of autografts, allografts, and nondegradable materials for bone replacement. They can be synthesized with tailored mechanical and degradative properties. They also can be processed to porous scaffolds with desired pore morphologic features conducive to tissue ingrowth. Moreover, functionalized polymers can modulate cellular function and induce tissue ingrowth. This review focuses on four classes of polymers that hold promise for orthopaedic applications: poly alpha-hydroxy esters, polyphosphazenes, polyanhydrides, and polypropylene fumarate crosslinked networks.

  1. Synthesis and characterizations of novel polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Chanthad, Chalathorn

    end-blocks is described for the first time. The synthetic strategy involves the preparation of the telechelic fluoropolymers using a functional benzoyl peroxide initiator as the macro-chain transfer agent for subsequent RAFT polymerization of the imidazolium methacrylate monomer. As revealed in DSC, SAXS and dielectric relaxation spectroscopy (DRS) measurements, there was no microphase separation in the triblock copolymers, likely due to solubility of ionic liquid moieties in the fluoropolymer matrix. The anionic counterion has direct impact on the thermal properties, ionic conductivity and segmental dynamics of the polymers. The temperature dependence of the ionic conductivity is well described by the Vogel-Tamman-Fulcher model, suggesting that ion motion is closely coupled to segmental motion. In Chapter 4 and 5, new solid electrolytes for lithium cations have been synthesized by catalyzed hydrosilylation reaction involving hydrogen atoms of polysiloxane and polyhedral oligomeric silsesquioxane (POSS) and double bonds of vinyl tris17-bromo-3,6,9,12,15- pentaoxaheptadecan-1-ol silane. The obtained structures are based on branched or dendritic with ionic liquid-ethylene oxide oligomer. High room temperature ionic conductivities have been obtained in the range of 10-4-10-5 can be regarded as solid electrolytes. This is attributed to the high concentration of ions from ionic liquid moieties in the tripodand molecule, high segmental mobility, and high ion dissociation from ethylene oxide spacers. The influence of anion structures and lithium salts and concentration has been investigated.

  2. A novel second-order non-linear optical coordination polymer with three-fold interpenetrated CdSO{sub 4}-type network constructed by carboxylate–sulfonate ligands and strontium ions

    SciTech Connect

    Guan, Lei; Wang, Ying

    2015-10-15

    A novel strontium carboxylate–sulfonate coordination polymer, [Sr(HSIP)(H{sub 2}O){sub 3}]{sub n·}nH{sub 2}O (1) (NaH{sub 2}SIP=5-sulfoisophthalic monosodium salt) has been synthesized by hydrothermal reaction. It was characterized by X-ray single crystal diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Each strontium atom is eight-coordinate with a distorted bicapped trigonal prismatic arrangement. The whole HSIP{sup 2−} ligand acts as a η{sup 5}μ{sup 4} bridge to generate three-fold interpenetrated CdSO{sub 4}-type network structure, which is constructed from the left- and right-handed helixes paralleled to each other bridged by the HSIP{sup 2−} ligands. The luminescence spectrum indicates an emission maximum at 459 nm. Compound 1 shows a second harmonic generation (SHG) response that is 4 times that of KH{sub 2}PO{sub 4}. - Graphical abstract: The whole HSIP{sup 2−} ligands act as η{sup 5}μ{sup 4} bridges with strontium ions, and the strontium ion is eight-coordinated, showing a distorted bicapped trigonal prism geometry. - Highlights: • A novel coordination polymer with a CdSO{sub 4}-type network structure was synthesized. • It shows a second harmonic generation response that is 4 times that of KH{sub 2}PO{sub 4}. • It is constructed from the helixes paralleled to each other.

  3. Solvent-controlled synthesis of tetranuclear cage-like copper(II) silsesquioxanes. Remarkable features of the cage structures and their high catalytic activity in oxidation with peroxides.

    PubMed

    Dronova, Marina S; Bilyachenko, Alexey N; Yalymov, Alexey I; Kozlov, Yuriy N; Shul'pina, Lidia S; Korlyukov, Alexander A; Arkhipov, Dmitry E; Levitsky, Mikhail M; Shubina, Elena S; Shul'pin, Georgiy B

    2014-01-14

    Two principally different in their molecular architecture isomeric tetranuclear copper(ii) silsesquioxanes, "Globule"-like compound [(PhSiO1.5)12(CuO)4(NaO0.5)4] (1) and "Sandwich"-like derivative [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (2), were synthesized by the partial cleavage of polymeric copper(ii) silsesquioxane [(PhSiO1.5)2(CuO)]n by tetraphenylcyclotetrasiloxanolate. The route leading to the formation of either 1 or 2 entirely depends on the nature and composition of the solvent used for this reaction. Thus, the process in an ethanol-1-butanol solution gives compound 1. When a 1,4-dioxane-methanol mixture was used, compound 2 was prepared. The structures and unusual crystal packing of the cages were confirmed by the X-ray studies. It has been found that the reaction of benzene with H2O2 in acetonitrile solution at 50 °C catalyzed by 1 requires addition of trifluoroacetic acid (TFA) in low concentration and gives phenol with a turnover number (TON) of 250 after 3 h. The initial reaction rate W0 linearly depends on the concentration of catalyst 2. The oxidation of 1-phenylethanol to acetophenone with hydrogen peroxide catalyzed by complex 1 in the presence of TFA is not efficient. In contrast, 1 exhibited excellent activity in the oxidation with tert-butyl hydroperoxide (TBHP) in the absence of any acid (the yield of acetophenone was close to the quantitative, TON attained 475 after 2 h). A kinetic study of this reaction led to the conclusion that the process occurs with the participation of radicals tert-BuO˙ produced in the Cu-promoted decomposition of TBHP. The mode of dependence of W0 on the initial concentration of TBHP indicates the formation of an intermediate adduct between the catalyst 1 and TBHP (characterized by the equilibrium constant K1≈ 2 M(-1) for the conditions of conducted experiments) followed by subsequent decomposition of the adduct (k2≈ 0.2 s(-1)) to generate an intermediate species tert-BuO˙ which induces the alcohol oxidation.

  4. Enhancing the electrical conductivity of a hybrid POSS-PCL/graphene nanocomposite polymer.

    PubMed

    Nezakati, Toktam; Tan, Aaron; Seifalian, Alexander M

    2014-12-01

    An electrically conductive polymer using polyhedral oligomeric silsesquioxane (POSS) nanocage incorporated into a modified poly [caprolactone based urea-urethane] (PCL)/graphene hybrid nanocomposite is described. Multilayer graphene flakes (8nm) were homogeneously dispersed into POSS-PCL at 0.1, 2, 5, and 10wt.% concentrations. This dispersion process of the graphene flakes was achieved by the use of stable dimethylacetamide (DMAc), via solution intercalation with POSS-PCL nanocomposites. The impedance spectroscopy of 5.0wt.% and higher concentration of graphene in POSS-PCL represented major improvement in conductivity over pristine POSS-PCL. The percolation threshold occurred at 5.0wt.% graphene concentration, converting the insulator POSS-PCL into a conductive POSS-PCL/graphene hybrid nanocomposite. The structures of the obtained hybrid materials were characterized with atomic force microscopy (AFM), Fourier transform infra-red (FT-IR), and Raman spectroscopy. The conductivity of the resultant nanocomposite polymer was investigated with electrochemical impedance spectroscopy (EIS). Herein, for the first time, we demonstrate a facile method of synthesizing, and describe the electrical properties of a conductive POSS-PCL/graphene nanocomposite polymer.

  5. Organometallic Polymers.

    ERIC Educational Resources Information Center

    Carraher, Charles E., Jr.

    1981-01-01

    Reactions utilized to incorporate a metal-containing moiety into a polymer chain (addition, condensation, and coordination) are considered, emphasizing that these reactions also apply to smaller molecules. (JN)

  6. Polymer flooding

    SciTech Connect

    Littmann, W.

    1988-01-01

    This book covers all aspects of polymer flooding, an enhanced oil recovery method using water soluble polymers to increase the viscosity of flood water, for the displacement of crude oil from porous reservoir rocks. Although this method is becoming increasingly important, there is very little literature available for the engineer wishing to embark on such a project. In the past, polymer flooding was mainly the subject of research. The results of this research are spread over a vast number of single publications, making it difficult for someone who has not kept up-to-date with developments during the last 10-15 years to judge the suitability of polymer flooding to a particular field case. This book tries to fill that gap. An indispensable book for reservoir engineers, production engineers and lab. technicians within the petroleum industry.

  7. Polymers All Around You!

    ERIC Educational Resources Information Center

    Gertz, Susan

    Background information on natural polymers, synthetic polymers, and the properties of polymers is presented as an introduction to this curriculum guide. Details are provided on the use of polymer products in consumer goods, polymer recycling, polymer densities, the making of a polymer such as GLUEP, polyvinyl alcohol, dissolving plastics, polymers…

  8. Chemistry of Silanes: Interfaces in Dental Polymers and Composites1

    PubMed Central

    Antonucci, Joseph M.; Dickens, Sabine H.; Fowler, Bruce O.; Xu, Hockin H. K.; McDonough, Walter G.

    2005-01-01

    The performance and service life of glass-or ceramic-filled polymeric composites depend on the nature of their resin, filler and interfacial phases as well as the efficacy of the polymerization process. The synergy that exists between the organic polymer matrix and the usually inorganic reinforcing filler phase is principally mediated by the interfacial/interphasial phase. This latter phase develops as a result of the dual reactivity of a silane coupling agent, (YRSiX3), a bifunctional molecule capable of reacting with the silanol groups of glass or ceramic fillers via its silane functional group (–SiX3) to form Si-O-Si- bonds to filler surfaces, and also with the resin phase by graft copolymerization via its Y functional group, usually a methacrylic vinyl group. In this paper, we explore some of the chemistry of organosilanes, especially that of functional organosilanes (or silane coupling agents as they are commonly known) that are used to mediate interfacial bonding in mineral reinforced polymeric composites. The chemistry of organosilanes can be quite complex involving hydrolytically initiated self-condensation reactions in solvents (including monomers) that can culminate in polymeric silsesquioxane structures, exchange reactions with hydroxylated or carboxylated monomers to form silyl ethers and esters, as well as the formation of silane derived interfaces by adhesive coupling with siliceous mineral surfaces. PMID:27308178

  9. Synthesis, Characterization and Properties of Chain Terminated Polyhedral Oligomeric Silsesquioxane-Functionalized Perfluorocyclobutyl Aryl Ether Copolymers (Preprint)

    DTIC Science & Technology

    2007-10-17

    deprotection and coupling with 4-(trifluorovinyloxy)benzoic acid. TFVE functionalized POSS monomers were thermally polymerized with 4,4’-bis(4...pyrolysis coupled with GC−MS. This initial weight loss was proportional to the weight percent POSS incorporated into the polymer. The balance of...with acetoxyethyltrichlorsilane followed by sequential acid-catalyzed deprotection and coupling with 4-(trifluorovinyloxy)benzoic acid. TFVE

  10. Recombinant protein polymers in biomaterials.

    PubMed

    Kim, Wookhyun

    2013-01-01

    Naturally occurring protein-based materials have been found that function as critical components in biomechanical response, fibers and adhesives. A relatively small but growing number of recombinant protein-based materials that mimic the desired features of their natural sources, such as collagens, elastins and silks, are considered as an alternative to conventional synthetic polymers. Advances in genetic engineering have facilitated the synthesis of repetitive protein polymers with precise control of molecular weights which are designed by using synthetic genes encoding tandem repeats of oligopeptide originating from a modular domain of natural proteins. Many repeat sequences as protein polymer building blocks adopt a well-defined secondary structure and undergo self-assembly to result in physically cross-linked networks or with chemical cross-linking so that further form three-dimensional architectures similar to natural counterparts. In this review, recombinant protein polymers currently developed will be presented that have emerged as promising class of next generation biomaterials.

  11. Rheological Analysis of Polymer Interactions and Ageing of Poly(Methylvinylether-Co-Maleic Anhydride)/Poly(Vinyl Alcohol) Binary Networks and Their Effects on Mucoadhesion.

    PubMed

    Andrews, Gavin P; Laverty, Thomas P; Jones, David S

    2015-12-01

    Polymer blends of poly(vinylalcohol, PVA) and poly(methylvinylether-co-maleic anhydride, PMVE/MA) were formulated and their viscoelastic and mucoadhesive properties characterised. The viscoelastic and mucoadhesive properties were dependent on polymer concentration, molecular weight of PVA and PVA:PMVE/MA ratio. Alteration of these properties allowed platforms to be designed to offer defined rheological and mucoadhesive properties, properties that could not be achieved using monopolymeric platforms. A strong correlation was noted between the modulus of the polymeric blends and mucoadhesion. After storage, the polymeric blends underwent rheological structuring (ageing) with an attendant enhancement of mucoadhesion. In certain blends containing the highest molecular weight of PVA (146-186 kDa), storage ultimately resulted in an increase and then a significant decrease in the rheological and mucoadhesive properties, the latter phenomenon being accredited to polymer recrystallisation. Ageing of the rheological and mucoadhesive properties was modelled using an exponential growth model, allowing predictions of the storage period associated with the maxima in viscoelastic and mucoadhesive properties. These observations highlight the possible implications whenever interactive polymeric blends are employed in drug delivery. Caution is therefore urged whenever a formulation strategy based on interactive polymer blends is employed to ensure that ageing is fully understood and mathematically characterised.

  12. Chromatographic efficiency comparison of polyhedral oligomeric silsesquioxanes-containing hybrid monoliths via photo- and thermally-initiated free-radical polymerization in capillary liquid chromatography for small molecules.

    PubMed

    Wang, Hongwei; Ou, Junjie; Liu, Zhongshan; Lin, Hui; Peng, Xiaojun; Zou, Hanfa

    2015-09-04

    Monolithic poly(methacrylate epoxy cyclosiloxane-co-polyhedral oligomeric silsesquioxanes) (epoxy-MA-POSS) capillary columns have been prepared via either photo- or thermally-initiated polymerization of the corresponding monomers using a 1-propanol/PEG 400 mixture as porogens. Photochemical polymerization was accomplished by irradiation of the UV-transparent capillary for 10min at room temperature, while thermal polymerization was performed at 55°C, 60°C or 65°C for 18h. The evaluation of chromatographic property for two hybrid epoxy-MA-POSS monoliths was carried out. The results indicate that hybrid monoliths fabricated by photochemical initiation exhibit higher column efficiency (97,000-98,400plates/m) than those synthesized by thermal polymerization (41,100-48,000plates/m) in cLC. The higher efficiency of photo-initiated hybrid monoliths is closely related to lower eddy dispersion (A-term) and mass transfer resistance (C-term).

  13. Hydrophobic interface controlled electrochemical sensing of nitrite based on one step synthesis of polyhedral oligomeric silsesquioxane/reduced graphene oxide nanocomposite.

    PubMed

    Bai, Wushuang; Sheng, Qinglin; Zheng, Jianbin

    2016-04-01

    In this paper, we report a novel hydrophobic interface controlled electrochemical sensing of nitrite based on polyhedral oligomeric silsesquioxane/ reduced graphene oxide nanocomposite (POSS/rGO). The POSS/rGO is prepared by one step hydrothermal synthesis method, and characterized by transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT-IR), Zeta-potential measurement analyzer, electrochemical impedance spectroscopy (EIS) and zero current potential method respectively. Then the POSS/rGO composite is used to fabricate electrochemical sensor for nitrite detection. According to experimental results, it is found that under control of hydrophobic force, the current peak will be shifted to lower potential (0.72 V) and the possible reason has been analyzed in manuscript. In addition, the POSS/rGO based sensor also has wide linear range (0.5 μM to 120 mM), low detection limit (0.08 μM) and good selectivity. In a word, the hydrophobic force controlled detection in this paper will provide a new platform for electrochemical sensing.

  14. Ethoxy and silsesquioxane derivatives of antimony as dopant precursors: unravelling the structure and thermal stability of surface species on SiO2.

    PubMed

    Alphazan, T; Florian, P; Thieuleux, C

    2017-03-14

    We report here the controlled preparation of SiO2 supported Sb-(mono)layers and their thorough characterization by in situ IR, solid-state NMR and elemental analyses. This study allows for the molecular understanding of the surface Sb species derived from the grafting of ethoxy and polyhedral oligomeric silsesquioxane antimony derivatives as mono- or bi-podal Sb(iii) surface species depending on the number of surface SiOH groups. This result is different from what was observed with the phosphorus analogue (POSS-P) that yielded P(v) species. A monolayer coverage of Sb species onto silica was also obtained using both POSS-Sb and the [Sb(OEt)3]2 derivative with surface densities ranging from ∼0.3 Sb nm(-2) to 1.8 Sb nm(-2), respectively. It is noteworthy that under optimized conditions, a layer of antimony species or suboxides on silica was produced using POSS-Sb without significant Sb loss, highlighting the protective properties of the POSS cage. These results open new perspectives for the controlled and non-destructive Sb-doping (Molecular Layer Doping) of semiconductors dedicated to nano-device applications.

  15. Photomotility of polymers

    PubMed Central

    Wie, Jeong Jae; Shankar, M. Ravi; White, Timothy J.

    2016-01-01

    Light is distinguished as a contactless energy source for microscale devices as it can be directed from remote distances, rapidly turned on or off, spatially modulated across length scales, polarized, or varied in intensity. Motivated in part by these nascent properties of light, transducing photonic stimuli into macroscopic deformation of materials systems has been examined in the last half-century. Here we report photoinduced motion (photomotility) in monolithic polymer films prepared from azobenzene-functionalized liquid crystalline polymer networks (azo-LCNs). Leveraging the twisted-nematic orientation, irradiation with broad spectrum ultraviolet–visible light (320–500 nm) transforms the films from flat sheets to spiral ribbons, which subsequently translate large distances with continuous irradiation on an arbitrary surface. The motion results from a complex interplay of photochemistry and mechanics. We demonstrate directional control, as well as climbing. PMID:27830707

  16. Photomotility of polymers

    NASA Astrophysics Data System (ADS)

    Wie, Jeong Jae; Shankar, M. Ravi; White, Timothy J.

    2016-11-01

    Light is distinguished as a contactless energy source for microscale devices as it can be directed from remote distances, rapidly turned on or off, spatially modulated across length scales, polarized, or varied in intensity. Motivated in part by these nascent properties of light, transducing photonic stimuli into macroscopic deformation of materials systems has been examined in the last half-century. Here we report photoinduced motion (photomotility) in monolithic polymer films prepared from azobenzene-functionalized liquid crystalline polymer networks (azo-LCNs). Leveraging the twisted-nematic orientation, irradiation with broad spectrum ultraviolet-visible light (320-500 nm) transforms the films from flat sheets to spiral ribbons, which subsequently translate large distances with continuous irradiation on an arbitrary surface. The motion results from a complex interplay of photochemistry and mechanics. We demonstrate directional control, as well as climbing.

  17. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2013-09-10

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  18. Porphyrin coordination polymer nanospheres and nanorods

    SciTech Connect

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2012-12-04

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  19. Antimocrobial Polymer

    DOEpatents

    McDonald, William F.; Huang, Zhi-Heng; Wright, Stacy C.

    2005-09-06

    A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from quaternary ammonium compounds, gentian violet compounds, substituted or unsubstituted phenols, biguanide compounds, iodine compounds, and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A)3P wherein A is hydroxyalkyl; and the antimicrobial agent is chlorhexidine, dimethylchlorophenol, cetyl pyridinium chloride, gentian violet, triclosan, thymol, iodine, and mixtures thereof.

  20. Antimicrobial Polymer

    DOEpatents

    McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2004-09-28

    A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The polymeric composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from metals, metal alloys, metal salts, metal complexes and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one example embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A).sub.3 P wherein A is hydroxyalkyl; and the metallic antimicrobial agent is selected from chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.