Science.gov

Sample records for block copolymer thin

  1. Rapid ordering of block copolymer thin films.

    PubMed

    Majewski, Pawel W; Yager, Kevin G

    2016-10-12

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times-hours or days-required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems. PMID:27537062

  2. Solvent enhanced block copolymer ordering in thin films

    NASA Astrophysics Data System (ADS)

    Misner, Matthew J.

    Diblock copolymer self-assembly of materials is emerging as a key element in the fabrication of functional nanostructured materials. By solvent casting or solvent annealing block copolymer thin films, we have demonstrated methods to produce diblock copolymer films with highly oriented, close-packed arrays of nanoscopic cylindrical domains with a high degree of long-range lateral order with few defects. The solvent imparts a high degree of mobility in the microphase-separated copolymer that enables a rapid removal of defects and a high degree of lateral order. Though the use of a selective cosolvent during solvent casting, it was found that the microdomain size and spacing could be increased, leading to a size-tunable system. Additionally, the presence of water also led to the ability to control the microdomain orientation during solvent annealing. Ionic complexation within cylinder-forming PS- b-EO block copolymer thin films was also investigated, where added salts bind PEO block as the minor component. Small amounts of added salts, on the order a few ions per chain, show large effects on the ordering of the copolymer films during solvent annealing. By using gold or cobalt salts, well-organized patterns of nanoparticles can be generated in the copolymer microdomains. Topographically and chemically patterned surfaces were used as a route to sectorizing and controlling the lattice orientation of copolymer films. Topographically patterned surfaces allow well-defined boundaries to confine the copolymer microdomains on a surface and effectively direct the ordering and grain orientation of the copolymer microdomains. Chemically patterned surfaces provide a route to direct the block copolymer ordering on completely flat surface, which may have advantages in applications where adding additional topography may be undesirable. To generate nanoporous templates from PS-b-PEO bases materials several routs were followed. The first route was through the addition and selective

  3. Orientation Distribution for Thin Film Block Copolymers

    NASA Astrophysics Data System (ADS)

    Jones, Ronald; Zhang, Xiaohua; Kim, Sangcheol; Karim, Alamgir; Briber, Robert; Kim, Ho-Cheol

    2008-03-01

    The directed self-assembly of nanostructured films with vertically oriented morphologies is a potential solution for manufacture of next generation data storage platforms, microelectronic devices, and nanoporous membranes. In many of these applications, the distribution of orientation must be tightly controlled to enable pattern transfer. This parameter is expected to depend on factors such as the Flory-Huggins chi parameter, but little data has been reported to date. We present results from tomographic small angle scattering on a series of block copolymer films whose assembly has been directed through solvent annealing. Films of poly(styrene-b-ethylene oxide) are cast as a function of annealing time and their orientation distribution reported. The results provide significant insight into the fundamental limits of line edge roughness and defect control possible using this fabrication technique.

  4. Nanostructured anion conducting block copolymer electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Arges, Christopher; Kambe, Yu; Nealey, Paul

    Lamellae forming block copolymer electrolyte (BCE) thin-films with perpendicular aligned orientation were registered with high fidelity over large areas via a self-assembly process followed by a novel chemical vapor infiltration reaction (CVIR) technique. In this scheme, poly(styrene- b-2-vinyl pyridine) (PS bP2VP) block copolymers were self-assembled with perpendicular orientations on neutral chemical brushes using solvent vapor annealing. The ionic groups were selectively introduced into the P2VP block via a Menshutkin reaction that converted the nitrogen in the pyridine to n-methylpyridinium - anion carrier groups. FTIR-ATR and XPS tools confirmed the formation of the aforementioned ionic moieties post CVIR process and structure imaging tools (e.g., SEM and AFM imaging, GI-SAXS and RSOXs) established that incorporation of the ionic groups did not alter the self-assembled nanostructured films nor did subsequent ion-exchange processes. Electrochemical impedance spectroscopy determined the in-plane ion conductivity of different counteranions in the BCE thin films and alteration to the symmetry of the block copolymer film substantially improved (or hindered) BCE ion conductivity if the P2VP block's volume fraction was slightly greater than (or less than) 0.5. U.S. Department of Energy, Office of Science under Contract No. DE-AC02-06CH11357.

  5. Self-assembled phases of block copolymer blend thin films.

    PubMed

    Yager, Kevin G; Lai, Erica; Black, Charles T

    2014-10-28

    The patterns formed by self-assembled thin films of blended cylindrical and lamellar polystyrene-b-poly(methyl methacrylate) block copolymers can be either a spatially uniform, single type of nanostructure or separate, coexisting regions of cylinders and lamellae, depending on fractional composition and molecular weight ratio of the blend constituents. In blends of block copolymers with different molecular weights, the morphology of the smaller molecular weight component more strongly dictates the resulting pattern. Although molecular scale chain mixing distorts microdomain characteristic length scales from those of the pure components, even coexisting morphologies exhibit the same domain spacing. We quantitatively account for the phase behavior of thin-film blends of cylinders and lamellae using a physical, thermodynamic model balancing the energy of chain distortions with the entropy of mixing. PMID:25285733

  6. Simple, generalizable route to highly aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Qiang, Zhe; Cavicchi, Kevin; Vogt, Bryan; University of Akron Team

    Macroscopic alignment of block copolymer domains in thin films is desired for many applications, such as cell responsive surfaces or optical polarizers. Alignment generally requires specialized tools that apply external fields, shear force gradient, or produce topological patterned substrates. This requirement limits the broad academic application of aligned BCPs. Here, we describe a simple modification of commonly utilized solvent vapor annealing (SVA) process for macroscopic alignment of BCPs. Adhering a flat, crosslinked elastomer pad to the BCP film leads to differential swelling between the elastomer pad and BCP to produce a shear force that aligns the ordered BCP domains. The role of elastomer properties, solvent quality, drying rate and degree of segregation of the block copolymer will be discussed to provide generalized rules for alignment with this technique. Cylindrical nanostructures formed in polystyrene-block-polydimethylsiloxane can be transformed into arrays of silica lines and increasing the thickness from a monolayer to bilayer can effectively halve the spacing of the lines. These results illustrate a generalized method for BCP alignment and a potential route for the generation of complex hierarchical assembled structures. A generalized method for block copolymer thin film alignment: solvent vapor annealing with shear.

  7. Highly-Ordered Thin Films from Photocleavable Block Copolymers

    NASA Astrophysics Data System (ADS)

    Gu, Weiyin; Zhao, Hui; Coughlin, E.; Theato, Patrick; Russell, Thomas; University of Massachusetts at Amherst Team; University of Hamburg Team

    2013-03-01

    A robust route for the preparation of nanoscopic dot/line patterns with long range lateral order from poly(styrene-block-ethylene oxide) (PS-b-PEO) with an o-nitrobenzyl ester junction (PS-h ν-PEO) is demonstrated. Solvent annealing condition is optimized to achieve the highly ordered cylindrical block copolymer (BCP) microdomains oriented normal or parallel to the silicon substrates. Following a very mild UV exposure and successive washing with methanol, PS-hv-PEO thin films were transformed into highly ordered porous or trench templates. Afterwards the pores or trenches were either filled with PDMS by spin-coating or exposed to direct metal deposition of Au. After a plasma etching or lift-off process to remove the polymer templates, highly ordered arrays of silica or Au nanopatterns were obtained. This represents the first template application example from highly ordered nanoporous thin films derived from block copolymers featuring a photocleavable junction. DOE (DE-FG02-96ER45612), NSF-MRSEC, DFG (TH 1104/4-1), CHE 0924435, R31-10013.

  8. Nanopatterning of ultrananocrystalline diamond thin films via block copolymer lithography.

    SciTech Connect

    Ramanathan, M.; Darling, S. B.; Sumant, A. V.; Auciello, O.

    2010-07-01

    Nanopatterning of diamond surfaces is critical for the development of diamond-based microelectromechanical system/nanoelectromechanical system (MEMS/NEMS), such as resonators or switches. Micro-/nanopatterning of diamond materials is typically done using photolithography or electron beam lithography combined with reactive ion etching (RIE). In this work, we demonstrate a simple process, block copolymer (BCP) lithography, for nanopatterning of ultrananocrystalline diamond (UNCD) films to produce nanostructures suitable for the fabrication of NEMS based on UNCD. In BCP lithography, nanoscale self-assembled polymeric domains serve as an etch mask for pattern transfer. The authors used thin films of a cylinder-forming organic-inorganic BCP, poly(styrene-block-ferrocenyldimethylsilane), PS-b-PFS, as an etch mask on the surface of UNCD films. Orientational control of the etch masking cylindrical PFS blocks is achieved by manipulating the polymer film thickness in concert with the annealing treatment. We have observed that the surface roughness of UNCD layers plays an important role in transferring the pattern. Oxygen RIE was used to etch the exposed areas of the UNCD film underneath the BCP. Arrays of both UNCD posts and wirelike structures have been created using the same starting polymeric materials as the etch mask.

  9. Functional Thin Films from Aligned Block Copolymers and Blends

    NASA Astrophysics Data System (ADS)

    Vogt, Bryan; Qiang, Zhe; Cavicchi, Kevin

    Block copolymer (BCP) self-assembly provides a simple, cost effective route to fabricating nanoscale patterns. Here we describe how we can modulate the alignment/orientation of BCP films using a modified solvent vapor anealing (SVA) method where the BCP is covered with an elastomer during SVA and controlled deswelling of the elastomer macroscopically produces a shear force that aligns the BCP domains. By proper selection of the BCP or BCP + functional precursors, functional nanopatterns can be obtained. Thin films of cylindrical forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) are shear aligned. High temperature calcination converts the PDMS to silica and removes the PS to yield the silica nanolines. The spacing of these features is effectively halved by the use of bilayer films. Sequential shear-alignment of two distinct layers can generate arbitrary line based nanostructured features such as a rhombic array, but the size of the features is defined by the BCP. Oligomeric phenolic resin can effectively modulate the size and morphology of amphiphilic BCPs even at high loadings (>70 wt

  10. Identification of block copolymers and determination of their purity by thin-layer chromatography.

    PubMed

    Gankina, E S; Efimova, I I; Kever, J J; Belenkii, B G

    1987-01-01

    The application of adsorption, precipitation and extraction thin-layer chromatography to the identification of block copolymers, determination of their homogeneity (mixtures of homopolymers), and evaluation of their compositional homogeneity by one- and two-dimensional, multistage and gradient methods, is described. To detect the polymers on the thin-layer plate, various methods of detection are used, including those specific for each component of the block copolymer. Examples of analysis of the following block copolymers by thin-layer chromatography are reported: PS-PMMA, PS-PB, PS-PAN, PS-PBG, PI-PMS-PI, PMMA-PBMA, PMMA-PBG, PS-PEO. PMID:18964274

  11. Defect motion and annihilation in block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Mueller, Marcus; Li, Weihua

    2015-03-01

    Using self-consistent field theory and computer simulation of a soft, coarse-grained particle model we study defect motion and annihilation in thin films of lamella-forming block copolymers on neutral and chemically patterned substrates. By virtue of the strain-field mediated interactions, dislocation defects with opposite orientation move towards each other. This motion depends both on the thermodynamic, strain-field mediated driving force and the single-chain dynamics that is required to alter the morphology and reduce the distance between the defect cores. This interplay results in a qualitative dependence of the time evolution on the topology of the defect morphology. Upon collision of the defects, they either spontaneously annihilate or form a metastable, tight defect pair. In the latter case, a free-energy barrier has to be overcome to finally produce a defect-free structure. Computing the minimum free-energy path within self-consistent field theory we investigate the dependence of the free-energy barriers of defect motion and annihilation on incompatibility, strength of the chemical surface pattern, and defect morphology. European Union FP7 / GA No. 619793 CoLiSA.MMP.

  12. Direct Immersion Annealing of Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Karim, Alamgir

    We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene -poly(methyl methacrylate) (PS -PMMA) system: rapid short range order, optimal long-range order, and a film instability regime. Kinetic studies in the ``optimal long-range order'' processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering. Inclusion of nanoparticles in these films at high concentrations and fast ordering kinetics study with neutron reflectivity and SANS will be discussed. This is (late) Contributed Talk Abstract for Dillon Medal Symposium at DPOLY - discussed with DPOLY Chair Dvora Perahia.

  13. Direct Immersion Annealing of Thin Block Copolymer Films.

    PubMed

    Modi, Arvind; Bhaway, Sarang M; Vogt, Bryan D; Douglas, Jack F; Al-Enizi, Abdullah; Elzatahry, Ahmed; Sharma, Ashutosh; Karim, Alamgir

    2015-10-01

    We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene-poly(methyl methacrylate) (PS-PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in the "optimal long-range order" processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering. PMID:26351823

  14. Confinement of block copolymers

    SciTech Connect

    1995-12-31

    The following were studied: confinement of block copolymers, free surface confinement, effects of substrate interactions, random copolymers at homopolymer interfaces, phase separation in thin film polymer mixtures, buffing of polymer surfaces, and near edge x-ray absorption fine structure spectroscopy.

  15. Surface Engineering of Styrene/PEGylated-Fluoroalkyl Styrene Block Copolymer Thin Films

    SciTech Connect

    Martinelle, E.; Menghetti, S; Galli, G; Glisenti, A; Krishnan, S; Paik, M; Ober, C; Smilgies, D; Fischer, D

    2009-01-01

    A series of diblock copolymers prepared from styrenic monomers was synthesized using atom transfer radical polymerization. One block was derived from styrene, whereas the second block was prepared from a styrene modified with an amphiphilic PEGylated-fluoroalkyl side chain. The surface properties of the resulting polymer films were carefully characterized using dynamic contact angle, XPS, and NEXAFS measurements. The polymer morphology was investigated using atomic force microscope and GISAXS studies. The block copolymers possess surfaces dominated by the fluorinated unit in the dry state and a distinct phase separated microstructure in the thin film. The microstructure of these polymers is strongly influenced by the thin film structure in which it is investigated.

  16. NEXAFS Depth Profiling of Surface Segregation in Block Copolymer Thin Films

    SciTech Connect

    Krishnan, S.; Paik, M; Ober, C; Martinelli, E; Galli, G; Sohn, K; Kramer, E; Fischer, D

    2010-01-01

    NEXAFS spectroscopy was used to probe the surface composition and under-water surface reconstruction of thin films of comb-like diblock copolymers with cylindrical and spherical microphases. The polymers consisted of a polystyrene block, and a second block prepared from a styrenic monomer grafted with fluoroalkyl-tagged poly(ethylene glycol) side chains. Compositional depth profiling of the microphase separated block copolymer films, in the top 1-3 nm of the film, was performed to understand the role of block copolymer microstructure and self-assembly on surface composition. Using experimentally determined concentration profiles, the surface concentration of phenyl ring carbon atoms was quantified and compared with those of homopolymer and random copolymer controls. The carbon atoms from the relatively high surface energy phenyl groups were depleted or excluded from the surface, in favor of the low surface-energy fluoroalkyl groups. While it is expected that block copolymer surfaces will be completely covered by a wetting lamellar layer of the lower surface energy block, a significant amount of the higher surface energy polystyrene block was found to be present in the surface region of the cylinder-forming block copolymer. Evidently, the spontaneous formation of the cylindrical polystyrene microdomains in the near-surface region compensated for the lowering of the free energy that could have been achieved by completely covering the surfaces with a lamellar layer of the lower surface energy fluorinated block. All surfaces underwent molecular reconstruction after immersion in water. The experimental concentration depth profiles indicated an increased surface depletion of phenyl ring carbon atoms in the water-immersed thin films, due to the tendency of hydrophilic PEG side groups to be present at the polymer-water interface. Such a detailed characterization of the outermost layers of the block copolymer surfaces was possible because of the exceptional depth resolution

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

    SciTech Connect

    Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; Chen, Jihua; Heller, William T.; Ankner, John F.; Browning, James F.; Kilbey, II, S. Michael; Sumpter, Bobby G.

    2015-02-03

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

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

    DOE PAGESBeta

    Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.; Chen, Jihua; Heller, William T.; Ankner, John F.; Browning, James F.; Kilbey, II, S. Michael; Sumpter, Bobby G.

    2015-02-03

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

  19. Macroscopic vertical alignment of nanodomains in thin films of semiconductor amphiphilic block copolymers.

    PubMed

    Brendel, Johannes C; Liu, Feng; Lang, Andreas S; Russell, Thomas P; Thelakkat, Mukundan

    2013-07-23

    Though several techniques have been reported on the alignment of conventional block copolymers, the macroscopic vertical orientation of semiconductor block copolymer microdomains in thin films has still not been accomplished. Here, we report the control on the alignment of nanostructures in a semiconductor amphiphilic block copolymer comprising an amorphous triphenyldiamine hole conductor block and a hydrophilic poly(styrene sulfonate) segment. Three different compositions with a hole conductor content of 57, 72, and 79 wt % were synthesized using a combination of controlled reversible addition/fragmentation transfer polymerization and "click" chemistry. All polymers feature a narrow molecular weight distribution. Cryo-TEM reveals the formation of micelles in DMF solutions of the amphiphilic copolymer having nanoscopic dimensions. The micelle size correlates well with the X-ray analysis of dried bulk samples. Atomic force microscopy (AFM) confirms the micellar structure in the as-cast films. Thermal annealing causes an aggregation of micelles but did not lead to morphologies known for conventional block copolymers. However, annealing in saturated DMF vapor induces a morphology transition and a vertical orientation of the microdomains which was determined by grazing incidence small-angle X-ray scattering and AFM. The morphology varies from lamella to cylinders with increasing content of the hole-conductor block. The orientation arises from the controlled evaporation of the solvent, a mechanism that is similar to that observed for conventional block copolymers. Our approach demonstrates the macroscopic vertical alignment of nanodomains in semiconductor block copolymers which is a key requirement for applications in hybrid devices. PMID:23746109

  20. PS-b-PDMS Block Copolymer Thin Film: Pattern Formation and Phase Behavior

    NASA Astrophysics Data System (ADS)

    Hsieh, I.-Fan; Cheng, Stephen Z. D.; Department of Polymer Science, The University of Akron Team

    2011-03-01

    Recently, block copolymer thin films attract great attention due to their potential applications in surface nano-lithography. In our work, PS- b -PDMS with cylinder morphology is chosen due to extremely large χ value between two blocks. Besides, PS- b -PDMS can be transformed into silicon oxide under UV/O3 exposure and a layer of silicon oxide with the self-assembled block copolymer patterns can be made. By utilizing the PGMEA as solvent, we can easily obtain sphere morphology in cylindrical composition block copolymer by preserved block copolymer solution morphology during film formation. Furthermore, in thermal annealing process, the phase behavior of the PS- b -PDMS thin film is strongly affects by molecular weight, film thickness and annealing temperature. In larger-molecular-weight PS- b -PDMS, we only observed spherical domains rearrangement and without morphology transition between sphere and cylinder due to high energy barrier, whereas, in the case of smaller-molecular-weight polymer, depending on the film thickness and annealing temperature, its thin film morphology transits between sphere and cylinder alternatively, which is similar to what we found in solvent annealing.

  1. Patterning square and rectangular arrays using shear-aligned block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Davis, Raleigh L.; Register, Richard A.; Gwyther, Jessica; Nunns, Adam; Manners, Ian; Chaikin, Paul M.

    2014-03-01

    Microphase separation of block copolymers in thin films can generate periodic structures: hexagonally packed arrays of dots from spherical or cylindrical phase block copolymers, or periodic stripes from cylindrical or lamellar phase block copolymers. Square or rectangular patterns, however, do not naturally form by spontaneous self-assembly of a simple diblock copolymer, and are a challenge to create. We present a simple way to create nano-square/rectangular arrays by building up a double-layer film of a cylinder-forming diblock, where each layer is sequentially deposited, shear-aligned independently, and cross-linked. Any block copolymer with at least one crosslinkable block can in principle be employed; in this study we use cylinder-forming polystyrene-b-poly(ferrocenylisopropylmethylsilane) and polystyrene-b-poly(hexylmethacrylate). The pitch of the array is tunable by varying polymer molecular weight. Oxygen reactive ion etching is used to reveal the grid structures, and these grids can in turn form nano-wells in the silicon substrate when the cylinder-forming block is very etch-resistant under the conditions used for silicon etching. Additionally, metal dots ordered in square arrays can be created using these grids as templates, via metal evaporation and lift-off.

  2. Microphase separation in thin films of lamellar forming poydisperse di-block copolymers

    DOE PAGESBeta

    Kumar, Rajeev; Kilbey, II, S Michael; Ankner, John Francis; Heller, William T; Chen, Jihua; Sides, Scott; Browning, Jim; Lokitz, Bradley S; Sumpter, Bobby G

    2015-01-01

    Microphase separation in thin films of lamellar forming polydisperse di-block copolymers is studied using self-consistent field theory (SCFT) and neutron reflectivity experiments. Diblock copolymers containing a polydisperse block (poly(glycidylmethacrylate) (PGMA)) connected to a near monodisperse block (poly(4,4-dimethyl-d6-2-vinylazlactone) (PVDMA-d6)) are considered in this work. Effects of chain length polydispersity, film thickness, substrate monomer and monomer-monomer interactions on the microphase segregation are studied using SCFT. The theoretical study reveals that an increase in polydispersity tends to decrease the number of lamellar strata that can be packed in a film of given thickness, in comparison to a film created with monodisperse di-block copolymers.more » This is a direct consequence of an increase in lamellar domain spacing with an increase in polydispersity index. These predictions are verified by comparison with neutron reflectity experiments done on thin films made from moderately polydisperse PGMA-b-PVDMA-d6 di-block copolymer deposited on silicon substrates. Furthermore, it is shown that polydispersity induces conformational asymmetry and an increase in the polydispersity index makes the polydisperse blocks less flexible in comparison with monodisperse blocks. It is shown that conformational asymmetry effects, which are entropic in origin and of increasing importance as film thickness descreases, drive the polydisperse blocks to the middle of the films despite favorable substrate interactions. Prediction of neutron reflectivity profiles using the SCFT provides a facile and robust route for model verification and leads to useful physical insights into behavior of di-block copolymers near interfaces.« less

  3. Silver based SERS substrates fabricated from block copolymer thin film

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Lee, Wonjoo; Lee, Seung Yong; Gao, Zhenghan; Rabin, Oded; Briber, R. M.

    2013-03-01

    Poly (styrene-block-4-vinyl pyridine) (PS-b-P4VP, Mw = 47-b-10 kDa, PDI =1.10) thin films were used to form large-scale long range ordered self-assembled hexagonal patterns of vertically P4VP oriented cylinders in a PS matrix on Si substrates. The P4VP cylindrical domains were crosslinked and quaternized using 1,4-dibromobutane. Negatively charged 15nm gold nanoparticles were attached to the quaternized P4VP domains through Coulombic interactions. Silver was then grown on the gold seeds to create nanometer scale gaps between the nanoparticles. The gap between the nanoparticles was fine tuned by controlling the silver growth time. The substrates showed large enhancement factors in the Raman scattering signal for a broad range of incident wavelengths. Present address: LG Chem Ltd, Information Technology & Electronic Materials R&D, Yuseong-gu Daejeon, South Korea

  4. PS-b-PDMS Block Copolymer Thin Film: Pattern Formation and Phase Behavior

    NASA Astrophysics Data System (ADS)

    Hsieh, I.-Fan; Cheng, Stephen Z. D.; Chen, Feng; Fu, Qiang

    2010-03-01

    Recently, block copolymer thin films are of great interest for their applications in surface patterning, and thin films of diblock copolymers with cylindrical microdomains normal to the surface are more attractive due to the tenability of large aspect ratios of the cylindrical microdomains. Within various kind of block copolymer, PS-b-PDMS is chosen due to an extremely large χ value between PS and PDMS. PS-b-PDMS can be transformed into silicon oxide under UV/O3 exposure, and a layer of silicon oxide with the self-assembled block copolymer patterns can be made. In our work, utilizing PGMEA as solvent and its vapor as spin casting atmosphere, we found an effective approach to obtain the PDMS cylinders oriented normal to the substrate. Furthermore, during benzene solvent annealing, PDMS cylinders' orientation transfers from perpendicular to parallel and then back to perpendicular again. By changing the cylinders orientation alternatively, the lateral order of cylinder packing gradually improved. By investigating this morphology evolution, the mechanism and free energy pathway for PS-b-PDMS thin film morphology transition during solvent annealing can be constructed.

  5. Microphase separated structures of block copolymer thin film with non-volatile selective solvent

    NASA Astrophysics Data System (ADS)

    Yamamoto, Katsuhiro; Umegaki, Naoya; Matsutani, Taito; Takagi, Hideaki; Ito, Eri; Sakurai, Shinichi

    2010-11-01

    Microphase separated structures of block copolymer, polystyrene-b-polyisoprene (PS-b-PI, phiPS = 14%) including non-volatile selective solvent thin films were investigated using grazing incidence small angle X-ray scattering technique. The diethyl phthalate (DEP) was used as a non-volatile selective solvent which solves PS only. The DEP swelled PS phase selectively and the microphase separated structure transited from the PS spherical domain to the lamellar domain with an increase in DEP content in the bulk state. Similarly, the phase separated structure in the thin film prepared by spin cast on a silicon wafer from the mixture of toluene/DEP and block copolymer changed according to the initial DPE concentration. However, the morphologies developed in the thin film were shifted to the structures at lower DEP concentration than that expected from the initial concentration. Moreover, the cylindrical and lamellar domains were aligned parallel and perpendicularly to the substrate, respectively.

  6. Hierarchical assembled nanostructures of hydrogen-bonded supramolecular block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Chen, Xiaofang; Cai, Yongchen

    Controlling the microdomain orientation and long-range ordering in block copolymer thin films is very important in a number of applications, such as nanotemplate, nanoporous thin film, and data storage media. The hierarchical assemblies of block copolymers PS- b-P4VP with dendronized small molecules (DM) hydrogen-bonded onto P4VP blocks were investigated in thin films after solvent vapor annealing. P4VP/DM could form lamellar or hexagonal columnar structure with the periodicity around 8 nm, depending on the stoichiometry of the complex. Hierarchical assemblies of PS- b-P4VP(DM)x, including lamellae-within-lamellae, cylinder-within-lamellae, and cylinder-within-cylinder, were simultaneously ordered and oriented in thin films, which have been studied systematically with the help of AFM, TEM and GISAXS technologies. The orientation of supramolecular assembly depends on the P4VP(DM) fraction and can be tailored by varying the DM to P4VP ratio. Structural transitions from cylinders of (P4VP/DM), lamellae, to cylinders of PS could be achieved by simply increasing the ratio of DM to 4VP units in block copolymer systems. This work was supported by the National Natural Science Foundation of China (21174003 and 21474073).

  7. Structure and Dynamics of Cylinder Forming Block Copolymers in Thin Films

    NASA Astrophysics Data System (ADS)

    Tsarkova, Larisa A.

    In this chapter, we present fundamental aspects of the phase behavior and ordering dynamics in thin films of compositionally asymmetric block copoly- mers. Cylinder-forming AB diblock and ABA triblock copolymers are used as model systems. In the introduction we briefly describe the physics which commonly governs block copolymer phase behavior both in bulk and in thin films; then we define characteristic features of thin film behavior with spe- cial emphasis on the parameters that are readily controlled in experiments. Along with the discussion of surface fields and confinement effects in Sect. 2, we focus on the issues that are seldom discussed in the literature such as molecular weight and molecular architecture effects on the phase behavior and on microdomain dynamics (Sect. 2), and the analysis of the characteristic microdomain dimensions (Sect. 3).We present measurements of the character- istic spacings and film thickness with sub-micron resolution and demonstrate confinement induced distortions of microdomain dimensions in thin films rela- tive to the respective parameters in bulk. In Sect. 4 we describe time-resolved details of structural ordering of cylinder microdomains which indicate that the dynamics of defect annihilation in block copolymer thin films is considerably more complex than anticipated so far.

  8. Shear-alignment of metal-containing block copolymer thin films for nanofabrication

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Register, Richard; Gwyther, Jessica; Manners, Ian; Chaikin, Paul

    2013-03-01

    Cylinder-forming block copolymers can be used as etch masks for the fabrication of nanowire grids, with both fine resolution and scalability. However, achieving a high aspect ratio in these nanostructures, where reactive ion etching is employed for pattern transfer, requires strong etch contrast between two blocks of the copolymer. We achieve this strong contrast by using metal-containing block copolymers: materials which either contain metal as synthesized, or which can be selectively metallized after deposition as thin films. In the first case, iron-containing polystyrene-b-poly(ferrocenylisopropylmethylsilane) (PS-PFS) forming PFS cylinders was employed, and a spin-coated film was aligned by shearing with a polydimethylsiloxane pad. In the second case, polystyrene-b-poly-2-vinylpyridine (PS-P2VP) was deposited as a film, shear-aligned, and then platinum was selectively sequestered within the P2VP cylinders by brief soaking in an aqueous solution of a Pt salt. In both cases, shear stress produced alignment over centimeter-scale areas; this alignment was retained for PS-P2VP during the selective metallization. The line pattern in these aligned block copolymer thin films is then transferred via reactive ion etching into amorphous silicon deposited onto a quartz wafer to fabricate silicon nanowire grid polarizers which can operate at deep ultraviolet wavelengths.

  9. Quantitative study of temperature-dependent order in thin films of cylindrical morphology block copolymer

    NASA Astrophysics Data System (ADS)

    Mishra, Vindhya; Kramer, Edward

    2010-03-01

    Disordering and defect generation in block copolymer systems at high temperatures is of significance to get a better understanding of the physics governing these systems, which can also direct efforts to minimize them. We have studied the smectic-nematic-isotropic transition in confined monolayers and bilayers of cylindrical morphology poly (styrene-b-2vinyl pyridine) diblock copolymer. Previous studies of melting phenomena in block copolymer thin films have relied on quantitative AFM studies alone. We have supplemented AFM studies with grazing incidence small angle X-ray diffraction lineshape analysis to quantify the decay of translational and orientational order with increasing temperature. The results have been interpreted in the context of the Toner-Nelson theory of melting for layered systems.

  10. Analysis of Order Formation in Block Copolymer Thin Films Using Resonant Soft X-Ray Scattering

    SciTech Connect

    Virgili, J.M.; Tao, Y.; Kortright, J.B.; Balsara, N.P.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley

    2007-07-13

    The lateral order of poly(styrene-block-isoprene) copolymer (PS-b-PI) thin films is characterized by the emerging technique of resonant soft X-ray scattering (RSOXS) at the carbon {pi}* resonance and compared to ordering in bulk samples of the same materials measured using conventional small-angle X-ray scattering. We show resonance using theory and experiment that the loss of scattering intensity expected with a decrease in sample volume in the case of thin films can be overcome by tuning X-rays to the {pi}* resonance of PS or PI. Using RSOXS, we study the microphase ordering of cylinder- and sphere-forming PS-b-PI thin films and compare these results to position space data obtained by atomic force microscopy. Our ability to examine large sample areas ({approx}9000 {micro}m{sup 2}) by RSOXS enables unambiguous identification of the lateral lattice structure in the thin films. In the case of the sphere-forming copolymer thin film, where the spheres are hexagonally arranged, the average sphere-to-sphere spacing is between the bulk (body-centered cubic) nearest neighbor and bulk unit cell spacings. In the case of the cylinder-forming copolymer thin film, the cylinder-to-cylinder spacing is within experimental error of that obtained in the bulk.

  11. Pattern formation and phase behavior in PS-B-Si containing block copolymer thin film

    NASA Astrophysics Data System (ADS)

    Hsieh, I.-Fan

    Since the top-down approaches, such as the extremely ultraviolet (EUV) technique and the high-index fluid-based immersion ArF lithography, may be cover one or two generations, these lithography technologies are getting more severe for the feature size scaling down to sub 10 nm. The directed self-assembly technology of block copolymers is one of the candidates for next generation lithography which can afford feature sizes that are dictated by the molecular weight of the block copolymer and are typically 15 to 30 nm. Directed self-assembly of block copolymers has attracted attention as a technology to extend photoresist-based lithography to smaller dimensions. It has been demonstrated that the directed self assembly of block copolymer offers a new route to perfect nanolithographic pattering at sub-50 nm length scale with molecular scale precision. For application in electronic media, it requires large-area, long-range ordered structures, which is both a kinetic and thermodynamic problem and requires subtle balance of various parameters and processing conditions. So far, block copolymer thin films have already achieved certain success, mainly with higher molecular weights and a feature size of ˜30 nm. Several challenges still remain, such as (a) the generation of long-range ordered structure with smaller feature sizes (domain size < 22 nm), (b) obtaining sharp interface between two domains with high lithographic contrast, particularly for smaller feature sizes, and (c) etch selectivity and resistance between two phases in the nanostructure. To address these challenges, several different approaches have been used in our research. First approach is using PS-b-PDMS. PDMS-containing block copolymers have emerged as next generation block copolymers for nanolithography. Their films can be processed under dry conditions using oxygen plasma to produce inorganic, silica patterns which enables their integration into existing device fabrication. Also, the large thermodynamic

  12. Morphology Development in Block Copolymer Thin Films via Direct Immersion Annealing

    NASA Astrophysics Data System (ADS)

    Modi, Arvind; Bhaway, Sarang; Vogt, Bryan; Sharma, Ashutosh; Karim, Alamgir

    2015-03-01

    Conventional methods of annealing thin block copolymer (BCP) films include Thermal Annealing and Solvent Vapor Annealing (SVA) processes. Both of the processes have demonstrated excellent control over morphologies and nanostructures. However, both have constraints including long annealing time duration and/or complicated setup requirement. We introduce Direct Immersion Annealing (DIA) of thin block copolymer (BCP) films involving immersion of polymer films directly into the solvent mixture composed of selective non-solvent and solvent for blocks. Non-solvent prevents the dissolution of films while the good solvent permeates the film and plasticizes the blocks. A fine control of swelling ratio can be achieved through an easy and robust control of solvent volume fractions. We studied cylindrical Poly(styrene-block-methyl methacrylate) system in detail and quantified the growth of correlation length (ξ) with time(t) [ ξ = Atn]. We observe a reduction in growth exponent (n) with several fold increase in pre-exponential factor (A) compared to isotropic thermal annealing. We further demonstrate the extension of this strategy to systems with diverse range of χ-parameter, molecular weight and other morphologies.

  13. Thin Isoporous Block Copolymer Membranes: It Is All about the Process.

    PubMed

    Hahn, Janina; Clodt, Juliana I; Abetz, Clarissa; Filiz, Volkan; Abetz, Volker

    2015-09-30

    The combination of the self-assembly of amphiphilic block copolymers and the nonsolvent induced phase inversion process offers an efficient way to isoporous integral-asymmetric membranes. In this context we report fast, easily upscalable and material reducing ways to thin self-assembled membranes. Therefore, we succeeded to implement a spray or dip coating step into the membrane formation process of different diblock copolymers like polystyrene-block-poly(4-vinylpyridine), poly(α-methylstyrene)-bock-poly(4-vinylpyridine), and polystyrene-block-poly(iso-propylglycidyl methacrylate). The formation of hexagonal pore structures was possible using a highly diluted one solvent system allowing the reduction of diblock copolymer consumption and therefore the production costs are minimized compared to conventional blade casting approaches. The broad applicability of the process was proven by using different flat and hollow fiber support materials. Furthermore, the membranes made by this new method showed a more than 6-fold increase in water flux compared to conventional polystyrene-block-poly(4-vinylpyridine) membranes with similar pore sizes prepared by blade casting. The membranes could be proven to be stable at transmembrane pressures of 2 bar and showed a pH responsive flux behavior over several cycles. PMID:26349610

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

    PubMed Central

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

    2015-01-01

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

  15. The role of tortuosity on ion conduction in block copolymer electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Kambe, Yu; Arges, Christopher G.; Nealey, Paul F.

    This talk discusses the role of grain tortuosity on ion conductivity in block copolymer electrolyte (BCE) thin films. In particular, we studied lamellae forming BCEs with both domains oriented perpendicular to the substrate surface and connected directly from one electrode to another - i.e., tortuosity of one. The BCE is composed of ion-conducting, poly(2-vinyl n-methylpyridinium) blocks and non-ionic polystyrene blocks. Prior to creating the BCE, the pristine block copolymer, poly(styrene- b-2-vinyl pyridine), was directly self-assembled (DSA) on topographical or chemical patterns via graphoepitaxy and chemoepitaxy. A chemical vapor infiltration reaction modified the P2VP block into positively charged, fixed quaternary ammonium groups paired with mobile counteranions. The graphoepitaxy process utilized topographical interdigitated gold nanoelectrodes (100s of nanometers spacing between electrodes) created via e-beam lithography. Alternatively, chemical patterns had gold electrodes incorporated into them with 10s to 100s of microns spacing using conventional optical lithography. The interdigitated gold electrodes enabled in-plane ion conductivity measurements of the DSA BCEs to study the role of grain tortuosity on ion conductivity. U.S. Department of Energy Office of Science: Contract No. DE-AC02-06CH11357.

  16. Directed Ordering of Block Copolymer Thin Films with Flexible Interfaces for Functional Materials

    NASA Astrophysics Data System (ADS)

    Karim, Alamgir

    2012-02-01

    Orientation control of block copolymer (BCP) films is important for advanced technological applications. We present studies on directed ordering of block copolymer thin films on rigid substrates such as quartz to elastomeric PDMS and flexible Kapton substrates for tunable orientation of microphase separated poly (styrene) -- block -poly (methylmethacrylate) (PS-PMMA) cylinder and lamellae forming BCP films. Although the crosslinked PDMS has low surface energy, its surface energy can be tuned by exposing to UV-Ozone (UVO) that presents an opportunity to change BCP-PDMS interfacial energy to control BCP orientation across full range of orientation and film wettability. On the other hand, Kapton offers a near neutral surface for PS-PMMA without surface modification. Via a modified version of a dynamic thermal processing termed cold zone annealing-sharp (CZA-S), we obtain a wide range of orientations of the block copolymer films in unfilled and nanoparticle filled systems with an interest in photovoltaic systems. With CZA-S, vertical orientation of PS-PMMA can be obtained in films as thick as 1 micron with etchable PMMA domains for membrane applications. GISAXS characterization of these etched BCP membranes reveals up to 5 orders of diffraction indicating hexagonally packed vertical nanopores that extend throughout the film. Under similar thermal gradient, but static conditions, temporally stable vertical cylinders form only within a narrow zone of maximum temperature gradient. Primary CZA-S ordering mechanism thus involves propagating this narrow vertically oriented zone of BCP cylinders created at the maximum thermal gradient section, across the film. An optimal speed is needed since the process competes with preferential surface wetting dynamics that favors parallel orientation. These results are reproduced on large area flexible films on a prototype dynamic R2R assembly platform with incorporated multi-CZA gradient for thin (100 nm) BCP films currently.

  17. Metal nanodot arrays fabricated via seed-mediated electroless plating with block copolymer thin film scaffolding

    NASA Astrophysics Data System (ADS)

    Komiyama, Hideaki; Iyoda, Tomokazu; Sanji, Takanobu

    2015-10-01

    We present an alternative approach to fabricating hexagonally arranged nanodot arrays of various metals by seed-mediated electroless plating with a cylinder-forming block copolymer thin film, PEO-b-PMA(Az), as a scaffold. Metal ions were selectively incorporated into PEO cylinders, followed by their reduction to metal and the etching of the scaffold to obtain highly ordered seed arrays of Au, Pd, and Pt. Nanodot arrays of the target metals (Au, Ag, and Ni) were selectively grown on the seed with their highly ordered arrangement by electroless plating. We studied the fabrication processes’ suitability for control of the nanodot array size, as well as the plasmonic properties thereof.

  18. Protein based Block Copolymers

    PubMed Central

    Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

    2011-01-01

    Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

  19. Synergistic templated self-assembly of cellulose nanocrystals in thin block copolymer films

    NASA Astrophysics Data System (ADS)

    Grolman, Danielle; Gilman, Jeffrey; Davis, Chelsea; Karim, Alamgir

    2015-03-01

    Nanofillers in thin polymer films offer unique advantage to potentially modify the film's thermal, optical, electrical and mechanical properties due to the high surface area to volume ratio and intrinsic property change at the nanoscale. Nanofilled polymer films have been shown to exhibit unusual film stability to dewetting with a nonmonotonic behavior with nanofiller loading, potentially arising from factors such as competitive phase behavior and filler aggregation, particularly in the high nanofiller concentration limit. In this regard, block copolymer films can act as ideal nanoscale structured templates to selectively sequester and organize nanofillers. In conjunction with incorporated cellulose nanocrystals (CNCs), we seek to understand how individual anisotropic nanofillers can provide synergistic reinforcement to inherently anisotropic nanostructured block copolymer films. A clear enhancement in the Young's Modulus was observed with increased CNC loading using strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) for thin films. To this end, we examine the nanoscale to microscale morphology of the blend film through AFM, TEM and grazing incidence small-angle x-ray scattering (GISAXS), and CNC dispersion and percolation through high-intensity grazing incidence wide-angle x-ray scattering (GIWAXS) analysis.

  20. Process Controlled Multiscale Morphologies in Metal-containing Block Copolymer Thin Films

    SciTech Connect

    Ramanathan, Nathan Muruganathan; Kilbey, II, S Michael; Darling, Seth B.

    2014-01-01

    Poly(styrene-block-ferrocenyldimethylsilane) (PS-b-PFS) is a metal-containing block copolymer that exhibits certain advantages as a mask for lithographic applications. These advantages include compatibility with a wide range of substrates, ease of control over domain morphologies and robust stability to etch plasma, which aid in the development of high-aspect-ratio patterns. An asymmetric cylinder-forming PS-b-PFS copolymer is subjected to different processing to manipulate the morphology of the phase-separated domains. Control of film structure and domain morphology is achieved by adjusting the film thickness, mode of annealing, and/or annealing time. Changing the process from thermal or solvent annealing to hybrid annealing (thermal and then solvent annealing in sequence) leads to the formation of mesoscale spherulitic and dendritic morphologies. In this communication, we show that reversing the order of the hybrid annealing (solvent annealing first and then thermal annealing) of relatively thick films (>100 nm) on homogeneously thick substrates develops disordered lamellar structure. Furthermore, the same processing applied on a substrate with a thin, mechanically flexible window in the center leads to the formation of sub-micron scale concentric ring patterns. Enhanced material mobility in the thick film during hybrid annealing along with dynamic rippling effects that may arise from the vibration of the thin window during spin casting are likely causes for these morphologies.

  1. Directed Self-Assembly of Block Copolymers in Thin Films on Polymer Nano-Stripes

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Eun; Kang, Ho-Jong; Lee, Dong Hyun; Nano Functional Materials Lab. Team

    In this study, we report directed self-assembly (DSA) of block copolymers in thin films on nano-stripes of polymers. Unique nano-stripes of poly(tetrafluoro ethylene) (PTFE) having ~20 nm of amplitude and ~200 nm of pitch were simply generated by physically rubbing a PTFE bar on various substrates like Si wafers, glass, and polyimide due to its low friction coefficient and high wear rate. The resulting nano-stripes were extremely oriented along the rubbing direction. Then, various asymmetric polystyrene-block-poly(2-vinylpyridine) copolymers (PS- b-P2VP) were directly self-assembled on the nano-stripes of PTFE by solvent-annealing in vapor of tetrahydrofuran (THF). As a result, PS- b-P2VP exhibited extremely ordered P2VP cylinders oriented normal to the surface in large area on the underlying nano-stripes of PTFE. In addition, as utilizing the BCPs as templates, hexagonal arrays of metal nanoparticles were generated in large area for further application. BCP thin films and arrays of metal nanoparticles were characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM).

  2. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns

    PubMed Central

    Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.; Mikael, Solomon; Suh, Hyo Seon; Liu, Chi-Chun; Geng, Dalong; Wang, Xudong; Arnold, Michael S.; Ma, Zhenqiang; Nealey, Paul F.

    2016-01-01

    Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces. PMID:27528258

  3. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns.

    PubMed

    Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M; Mikael, Solomon; Suh, Hyo Seon; Liu, Chi-Chun; Geng, Dalong; Wang, Xudong; Arnold, Michael S; Ma, Zhenqiang; Nealey, Paul F

    2016-01-01

    Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces. PMID:27528258

  4. Structured block copolymer thin film composites for ultra-high energy density capacitors

    NASA Astrophysics Data System (ADS)

    Samant, Saumil; Hailu, Shimelis; Grabowski, Christopher; Durstock, Michael; Raghavan, Dharmaraj; Karim, Alamgir

    2014-03-01

    Development of high energy density capacitors is essential for future applications like hybrid vehicles and directed energy weaponry. Fundamentally, energy density is governed by product of dielectric permittivity ɛ and breakdown strength Vbd. Hence, improvements in energy density are greatly reliant on improving either ɛ or Vbd or a combination of both. Polymer films are widely used in capacitors due to high Vbd and low loss but they suffer from very low permittivities. Composite dielectrics offer a unique opportunity to combine the high ɛ of inorganic fillers with the high Vbd of a polymer matrix. For enhancement of dielectric properties, it is essential to improve matrix-filler interaction and control the spatial distribution of fillers for which nanostructured block copolymers BCP act as ideal templates. We use Directed Self-assembly of block copolymers to rapidly fabricate highly aligned BCP-TiO2 composite nanostructures in thin films under dynamic thermal gradient field to synergistically combine the high ɛ of functionalized TiO2 and high Vbd of BCP matrix. The results of impact of BCP morphology, processing conditions and concentration of TiO2 on capacitor performance will be reported. U.S. Air Force of Scientific Research under contract FA9550-12-1-0306

  5. Subnanometer Porous Thin Films by the Co-assembly of Nanotube Subunits and Block Copolymers

    SciTech Connect

    Xu, Ting; Zhao, Nana; Ren, Feng; Hourani, Rami; Lee, Ming Tsang; Shu, Jessica Y; Mao, Samuel; Helms, Brett A

    2011-02-22

    Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation and protective coatings. While molecularly defined nanoporous inorganic and organic materials abound, generating flexible nanoporous thin films with highly aligned channels over large areas has been elusive. Here, we developed a new approach where the growth of cyclic peptide nanotubes can be directed in a structural framework set by the self-assembly of block copolymers. By conjugating polymers to cyclic peptides, the subunit of an organic nanotube can be selectively solubilized in one copolymer microdomain. The conjugated polymers also mediate the interactions between nanotube and local medium and guide the growth of nanotubes in a confined geometry. This led to subnanometer porous membranes containing high-density arrays of through channels. This new strategy takes full advantage of nanoscopic assembly of BCPs and the reversibility of organic nanotube growth and circumvents impediments associated with aligning and organizing high aspect ratio nano-objects normal to the surface. Furthermore, the hierarchical coassembly strategy described demonstrates the feasibility of synchronizing multiple self-assembly processes to achieve hierarchically structured soft materials with molecular level control.

  6. Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films

    SciTech Connect

    Tung, Shih-Huang; Kalarickal, Nisha C.; Mays, Jimmy W.; Xu, Ting

    2009-09-08

    The hierarchical assemblies of supramolecules, which consisted of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) with 3-pentadecylphenol (PDP) hydrogen-bonded to the 4VP, were investigated in thin films after solvent annealing in a chloroform atmosphere. The synergistic coassembly of PS-b-P4VP and PDP was utilized to generate oriented hierarchical structures in thin films. Hierarchical assemblies, including lamellae-within-lamellae and cylinders-within-lamellae, were simultaneously ordered and oriented from a few to several tens of nanometers over macroscopic length scales. The macroscopic orientation of supramolecular assembly depends on the P4VP(PDP) fraction and can be tailored by varying the PDP to P4VP ratio without interfering with the supramolecular morphologies. The lamellar and cylindrical microdomains, with a periodicity of {approx}40 nm, could be oriented normal to the surface, while the assembly of comb blocks, P4VP(PDP), with a periodicity of {approx}4 nm, were oriented parallel to the surface. Furthermore, using one PS-b-P4VP copolymer, thin films with different hierarchical structures, i.e., lamellae-within-lamellae and cylinders-within-lamellae, were obtained by varying the ratio of PDP to 4VP units. The concepts described in these studies can be potentially applied to other BCP-based supramolecular thin films, thus creating an avenue to functional, hierarchically ordered thin films.

  7. Thin polymer films of block copolymers and blend/nanoparticle composites

    NASA Astrophysics Data System (ADS)

    Kalloudis, Michail

    In this thesis, atomic force microscopy (AFM), transmission electron microscopy (TEM) and optical microscopy techniques were used to investigate systematically the self-assembled nanostructure behaviour of two different types of spin-cast polymer thin films: poly(isoprene-b-ethylene oxide), PI-b-PEO diblock copolymers and [poly(9,9-dioctylfluorene-co-benzothiadiazole)]:poly[9,9- dioctyfluorene-co-N-(4-butylphenyl)-diphenylamine], F8BT:TFB conjugated polymer blends. In the particular case of the polymer blend thin films, the morphology of their composites with cadmium selenide (CdSe) quantum dot (QD) nanoparticles was also investigated. For the diblock copolymer thin films, the behaviour of the nanostructures formed and the wetting behaviour on mica, varying the volume fraction of the PEO block (fPEO) and the average film thickness was explored. For the polymer blend films, the effect of the F8BT/TFB blend ratio (per weight), spin-coating parameters and solution concentration on the phase-separated nanodomains was investigated. The influence of the quantum dots on the phase separation when these were embedded in the F8BT:TFB thin films was also examined. It was found that in the case of PI-b-PEO copolymer thin films, robust nanostructures, which remained unchanged after heating/annealing and/or ageing, were obtained immediately after spin coating on hydrophilic mica substrates from aqueous solutions. The competition and coupling of the PEO crystallisation and the phase separation between the PEO and PI blocks determined the ultimate morphology of the thin films. Due to the great biocompatible properties of the PEO block (protein resistance), robust PEO-based nanostructures find important applications in the development of micro/nano patterns for biological and biomedical applications. It was also found that sub-micrometre length-scale phase-separated domains were formed in F8BT:TFB spin cast thin films. The nanophase-separated domains of F8BT-rich and TFB-rich areas

  8. Role of defects on self-assembly of nanoparticles in block copolymer thin film

    NASA Astrophysics Data System (ADS)

    Kim, Jenny; Green, Peter

    2011-03-01

    The structure of A-b-B block copolymer (BCP) thin films is often exploited as scaffolds for directing nanoparticles into various, long-range ordered geometries. Depending on the affinity between nanoparticles and block chains, nanoparticles preferentially segregate to either A or B domains. We show that dislocations may play a dominant role in the assembly of large nanoparticles in BCP thin film that order at suboptimal thicknesses. Edge dislocations are ubiquitous in lamellar BCP thin films forming a partial surface layer, i.e. holes or island structures. When the ratio of the nanoparticle diameter, d, to the domain dimension, L, d/L 0.15, the nanoparticles were distributed uniformly throughout the film. However for larger values of d/L, the nanoparticles reside primarily at the dislocation cores. In the case of films of initial film thicknesses between L h < 3L the nanoparticles self-assemble into 2-dimensional planar shapes at the boundaries of holes or islands where edge dislocations are located.

  9. Nanoporous membrane based on block copolymer thin film for protein drug delivery

    NASA Astrophysics Data System (ADS)

    Yang, Seung Yun; Yang, Jeong-A.; Kim, Eung-Sam; Jeon, Gumhye; Oh, Eun Ju; Choi, Kwan Yong; Hahn, Sei Kwang; Kim, Jin Kon

    2010-03-01

    We studied long term and controlled release of protein drugs by using nanoporous membranes with various pore sizes. Nanoporous membrane consists of the separation layer prepared by polystyrene-block-poly(methylmethacrylate) copolymer thin film and conventional microfiltration membrane as a support. We demonstrate a long-term constant in vitro release of bovine serum albumin (BSA)and human growth hormone ) (hGH) without their denaturation up to 2 months. A nearly constant serum concentration of hGH was maintained up to 3 weeks in SD rats. The long-term constant delivery based on this membrane for protein drugs within the therapeutic range can be highly appreciated for the patients with hormone- deficiency.

  10. Co-assembly of polymer covered cyclic peptide nanotubes and block copolymer in thin films

    NASA Astrophysics Data System (ADS)

    Zhang, Chen; Lazzara, Thomas; Li, Changyi; Helmes, Brett; Xu, Ting

    2013-03-01

    Nanotubular structures have gained prevalent interest for their unique hollow structures and high aspect ratio and their potential applications ranging from molecular separation to nanocomposite membranes. We used nanotube forming cyclic peptide (CP) as the structural motif and studied the self-assembly of polymer conjugated CPs in block copolymer (BCP) matrix in thin films. The co-assembly process is mainly driven by thermodynamic quantities, namely Flory-Huggins polymer-polymer interactions that governs the interaction between CP and BCP, interfacial interactions that affects polymer chain orientation, and thin film commensurability. In addition, due to the dynamic nature of the nanotube formation, the co-assembly process is also pathway-dependent. Thus, processing conditions are critical in co-assembling CP nanotubes and BCP in thin films. Our result shows that the initial aggregation state of polymer covered CP nanotubes determines the pathway the system takes and hence the final morphology of the films. The co-assembly of polymer-conjugated CPs and BCPs demonstrates the feasibility of assembling 1D nanotubes in supramolecular thin films and opens up a new avenue for the generation of novel nanotubular structures.

  11. Photocontrol over the Disorder-to-Order Transition (DOT) in Thin Film of Polystyrene-block-Poly(methyl methacrylate) Block Copolymers Containing Photodimerizable anthracene functionality

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Li, Le; Wei, Xinyu; Balazs, Anna; Matyjaszewski, Krzysztof; Russell, Thomas

    2010-03-01

    Reversible photocontrol over the disorder-to-order transition (DOT) of block copolymers can be used to fabricate defect-free, long-range ordered nanomaterials over macroscopic distances by ``photo-combing'' the microdomains. Here, we randomly copolymerized anthracene functionalities in a ``dilute'' way with 2-hydroxyethyl methacrylate as the middle block, forming deuterated polystyrene-block-poly(2-(methacryloyloxy)ethyl anthracene-9-carboxylate-random-2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) (d8-PS-b-P(9AnEMA-r-HEMA)-b-PMMA) triblock copolymers. Upon UV irradiation of a thin film of the phase-mixed triblock copolymer, photodimerization of anthracene links the junction of d8-PS and PMMA blocks and produces an artificial interface to force a phase-separation, i.e. a UV-induced DOT, as evidenced by small angle neutron scattering (SANS). Reversible photocontrol over the DOT can be achieved by taking advantage of photodimerization and photodissociation of anthracene.

  12. Lubricating effect of thin films of styrene-dimethylsiloxane block copolymers

    SciTech Connect

    Ndoni, S.; Jannasch, P.; Larsen, N.B.; Almdal, K.

    1999-05-25

    The lubricating effect of styrene-dimethylsiloxane block copolymer films spin cast on Si wafers was found to increase with increasing size of the poly(dimethylsiloxane) (PDMS) block. Friction properties of symmetrical and close-to-symmetrical block copolymers were evaluated in contact with bromobutyl rubber in a plate-on-plate configuration. X-ray photoelectron spectroscopy showed that the copolymer films were all covered by at least a 10 nm thick layer of PDMS. The lubricating effect remained constant down to a film thickness comparable to the chain dimensions of the copolymer, R{sub 0}, after which it decreased progressively. At thicknesses below R{sub 0}, the copolymer dewetted the wafer and formed discrete domains with sizes comparable to R{sub 0}. The copolymer could further be blended with up to 70 wt % polystyrene without detecting a decrease in the lubricating effect. A mechanism is proposed for the observed frictional behavior where microflakes are abraded from lamellar copolymer surfaces and stick to the contacting rubber surface, whereafter lubrication may result from sliding of PDMS brushes against each other.

  13. Manipulating block copolymer self-assemblies in bulk and thin films by thermal and solvent annealing

    NASA Astrophysics Data System (ADS)

    Gu, Weiyin

    The self--assembly of block copolymers (BCPs) into well--ordered nanoscopic arrays holds promise for new technological breakthroughs as templates and scaffolds for the fabrication of nanostructured materials. It is essential to establish convenient approaches to control the morphology of BCPs, since some applications require addressability, the BCP microdomains must be perfectly aligned and oriented. The theme of this thesis is the use of external forces, specifically thermal and solvent annealing, to guide the self--assembly of BCPs to obtain microphase separated morphologies for different applications. Three representative BCP systems, having lamellar, cylindrical and spherical microdomains are discussed. First, the self--assembly of lamella--forming brush block copolymers (BrBCPs) having polylactide (PLA) and polystyrene (PS) side chains were studied in the bulk and in thin films. The domain size increased approximately linearly with the molecular weight of the backbone, which indicated that the backbone was in an extended conformation that was confirmed theoretically. In situ small angle x--ray scattering (SAXS) measurements indicated that the self--assembly of the BrBCPs was quite rapid, due to the rigid nature of the backbone chain, Second, the directed self--assembly of cylinder--forming polystyrene--block--poly(ethylene oxide)s (PS--b--PEOs) in thin films were investigated. The polymer--surface interactions were tuned by hydroxyl end--functionalized polymers, so that the orientation of the PS--b--PEO microdomains was controlled during thermal annealing. Cylindrical PEO microdomains embedded in a PS matrix orientated normal to the silicon substrates were observed over a wide processing window when the substrates were modified by PS-- b--PEO BCPs. PS--b--PEOs with an o--nitrobenzyl ester junction point (PS--hnu --PEOs) were used to fabricate nanoscopic dot and line patterns having long--range lateral order. The cylindrical BCP microdomains were oriented

  14. Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers

    SciTech Connect

    Vu, Thai; Mahadevapuram, Nikhila; Perera, Ginusha M.; Stein, Gila E.

    2012-03-15

    Domain orientations in thin films of lamellar copolymers are evaluated as a function of copolymer architecture, film thickness, and processing conditions. Two copolymer architectures are considered: An AB diblock of poly(styrene-b-methyl methacrylate) and an ABA triblock of poly(methyl methacrylate-b-styrene-b-methyl methacrylate). All films are cast on substrates that are energetically neutral with respect to the copolymer constituents. Film structures are evaluated with optical microscopy, atomic force microscopy, and grazing-incidence small-angle X-ray scattering. For AB diblock copolymers, the domain orientations are very sensitive to film thickness, annealing temperature, and imperfections in the 'neutral' substrate coating: Diblock domains are oriented perpendicular to the substrate when annealing temperature is elevated ({>=} 220 C) and defects in the substrate coating are minimized; otherwise, parallel or mixed parallel/perpendicular domain orientations are detected for most film thicknesses. For ABA triblock copolymers, the perpendicular domain orientation is stable for all the film thicknesses and processing conditions that were studied. The orientations of diblock and triblock copolymers are consistent with recent works that consider architectural effects when calculating the copolymer surface tension (Macromolecules 2006, 39, 9346 and Macromolecules 2010, 43, 1671). Significantly, the data demonstrate that triblocks are easier to process for applications in nanopatterning - in particular, when high-aspect-ratio nanostructures are required. However, both diblock and triblock films contain a high density of 'tilted' or bent domains, and these kinetically trapped defects should be minimized for most patterning applications.

  15. Automated Defect and Correlation Length Analysis of Block Copolymer Thin Film Nanopatterns

    PubMed Central

    Murphy, Jeffrey N.; Harris, Kenneth D.; Buriak, Jillian M.

    2015-01-01

    Line patterns produced by lamellae- and cylinder-forming block copolymer (BCP) thin films are of widespread interest for their potential to enable nanoscale patterning over large areas. In order for such patterning methods to effectively integrate with current technologies, the resulting patterns need to have low defect densities, and be produced in a short timescale. To understand whether a given polymer or annealing method might potentially meet such challenges, it is necessary to examine the evolution of defects. Unfortunately, few tools are readily available to researchers, particularly those engaged in the synthesis and design of new polymeric systems with the potential for patterning, to measure defects in such line patterns. To this end, we present an image analysis tool, which we have developed and made available, to measure the characteristics of such patterns in an automated fashion. Additionally we apply the tool to six cylinder-forming polystyrene-block-poly(2-vinylpyridine) polymers thermally annealed to explore the relationship between the size of each polymer and measured characteristics including line period, line-width, defect density, line-edge roughness (LER), line-width roughness (LWR), and correlation length. Finally, we explore the line-edge roughness, line-width roughness, defect density, and correlation length as a function of the image area sampled to determine each in a more rigorous fashion. PMID:26207990

  16. Continuous and patterned deposition of functional block copolymer thin films using electrospray

    NASA Astrophysics Data System (ADS)

    Toth, Kristof; Hu, Hanqiong; Kim, Myungwoong; Gopalan, Padma; Loewenberg, Michael; Osuji, Chinedum

    The delivery of sub-micron droplets of dilute polymer solutions to a heated substrate by electrospray deposition (ESD) enables precisely controlled and continuous growth of block copolymer (BCP) thin films. The ESD process overcomes many shortcomings of spin coating deposition, including the batch nature of the process, loss of potentially valuable polymer, limitations of solvent choice, and large time scales of annealing. We report that high substrate temperatures led to vertically oriented cylindrical microdomains of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) at the film surface independent of the solvent composition and deposition rates utilized. Conversely, low substrate temperatures resulted in morphologies that were more sensitive to these parameters, with poorly ordered films of globular structures. We also report on the new possibility for patterned deposition of BCP films by spatially varying the electric field at the substrate using an underlying charged grid. To overcome surface charging, a novel alternating current electrospray process is proposed for deposition on non-conductive surfaces.

  17. Heterogeneous patterns on block copolymer thin film via solvent annealing: Effect on protein adsorption

    NASA Astrophysics Data System (ADS)

    Shen, Lei; Zhu, Jintao; Liang, Haojun

    2015-03-01

    Heterogeneous patterns consisting of nanometer-scaled hydrophobic/hydrophilic domains were generated by self-assembly of poly(styrene)-block-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA) block copolymer thin film. The effect of the heterogeneity of the polymer film surface on the nonspecific adsorption of the protein human plasma fibrinogen (FBN, 5.0 × 5.0 × 47.5 nm3) was investigated. The kinetics of the FBN adsorption varies from a single-component Langmuir model on homogeneous hydrophilic PHEMA to a two-stage spreading relaxation model on homogeneous hydrophobic PS surface. On a heterogeneous PS-b-PHEMA surface with majority PS part, the initial FBN adsorption rate remains the same as that on the homogeneous PS surface. However, hydrophilic PHEMA microdomains on the heterogeneous surface slow down the second spreading stage of the FBN adsorption process, leading to a surface excess of adsorbed FBN molecules less than the presumed one simply calculated as adsorption onto multiple domains. Importantly, when the PS-b-PHEMA surface is annealed to form minority domelike PS domains (diameter: ˜50-100 nm) surrounded by a majority PHEMA matrix, such surface morphology proves to be strongly protein-repulsive. These interesting findings can be attributed to the enhancement of the spread FBN molecule in a mobile state by the heterogeneity of polymer film surface before irreversible adsorption occurs.

  18. Formation of Lamellar Heterolattices in Block Copolymer Thin Films by Sequential Electrospray Deposition

    NASA Astrophysics Data System (ADS)

    Choo, Youngwoo; Hu, Hanqiong; Toth, Kristof; Osuji, Chinedum

    Electrospray deposition (ESD) of block copolymers (BCPs) on a heated substrate provides precise control over the formation of BCP thin films. This continuous deposition process allows one to fabricate heterogeneously assembled thin films by altering the deposition materials. Here, we demonstrate such the sequential ESD of lamellae-forming poly(styrene- b-4-vinylpyridine) BCPs with differing molecular weights and explore the morphology of the composite films. The resulting structure of the heterolattice interface was a strong function of temperature. Sharp interfaces with abrupt changes in the lamellar period (L0) were observed at lower deposition temperatures (150 - 170 °C), while higher temperature (190 °C) produced a smooth variation in the lamellar period from one molecular weight to the next. Furthermore, the ordering kinetics of a secondary layer which was deposited onto the primary layer could be substantially enhanced depending on the molecular weight of the polymer present in the underlying primary layer. We elucidate these findings in the context of temperature and molecular weight dependent diffusion dynamics of the polymers in the melt which control the inter-mixing of the layers. We gratefully acknowledge funding by NSF DRM-1410568.

  19. Rapid thermal processing of self-assembling block copolymer thin films on flat surfaces and topographically defined patterns

    NASA Astrophysics Data System (ADS)

    Perego, Michele; Ferrarese Lupi, Federico; Giammaria, Tommaso J.; Seguini, Gabriele; Gianotti, Valentina; Antonioli, Diego; Sparnacci, Katia; Laus, Michele; Enrico, Emanuele; de Leo, Natascia; Boarino, Luca; Ober, Christopher K.

    2014-03-01

    Self-assembling block copolymers generate nanostructured patterns, which are potentially useful for a wide range of applications. However, their technological implementation is prevented by the very long time required to drive the process. In this contribution, we demonstrate the capability to control the morphology of the self-assembling process of cylinder forming PS-b-PMMA diblock copolymer (DBC) thin films deposited on un-patterned and topographically patterned surfaces by means of a Rapid Thermal Processing (RTP) machine. Highly ordered patterns were obtained on flat surfaces for perpendicular-oriented cylindrical PS-b-PMMA block copolymers in less than 60 s. The BCs morphology evolution within topographically defined structures was systematically investigated as well. Irrespective of the surface neutralization, an irreversible orientational flipping of the BCP microdomains inside the trenches was observed. This effect was attributed to de-swelling of the polymeric film as a consequence of a progressive desorption of the solvent retained inside the film.

  20. Surface effects on the structure of block copolymer and homopolymer thin films

    NASA Astrophysics Data System (ADS)

    Sohn, Karen E.

    One strategy for producing effective fouling release surfaces for ship hulls is to use a bilayer system with a thermoplastic elastomer with a tunable modulus as the bottom layer and a surface active block copolymer (SABC) to control the surface chemistry. SABC's with semifluorinated liquid crystal side chains are used to minimize surface adhesion by fouling agents. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to characterize the structure of the liquid side crystal side chains. A method for depth profiling using NEXAFS spectroscopy where the post-edge intensities are fit and used to measure the thickness of the perfluoroalkyl surface layer. The Auger electron escape depth was determined to be 1.61nm, and the thickness of the perfluoroalkyl surface layer of a polystyrene homopolymer functionalized with perfluorinated alkyl chains is 0.42nm. A possible thermoplastic elastomer for the underlayer is poly(styrene-b-ethylener-butylene-b-styrene) (SEBS). The modulus can be adjusted by varying the composition of the block copolymer. The SEBS studied here has a bulk order-order transition (OOT) that transforms the morphology from hexagonally packed cylinders to body centered cubic (BCC) spheres as the temperature is increased. The thin film behavior is studied with atomic force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS). In thin films annealed both above and below the OOT, the morphology is always spherical. When the film contains less than 4 layers of spheres, they are packed on a hexagonal lattice. The packing transition from hexagonal packing to face centered orthorhombic packing occurs when there are 4 layers of spheres. The morphology is always spherical over the thickness range studied here because of the free energy penalty due to looping of the midblock, which is required for the surface to be covered by the lower surface energy PEB. The percentage of midblock chains that must loop is lower for spheres

  1. Bactericidal block copolymer micelles.

    PubMed

    Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo

    2011-05-12

    Block copolymer micelles with bactericidal properties were designed to deactivate pathogens such as E. coli bacteria. The micelles of PS-b-PAA and PS-b-P4VP block copolymers were loaded with biocides TCMTB or TCN up to 20 or 30 wt.-%, depending on the type of antibacterial agent. Bacteria were exposed to loaded micelles and bacterial deactivation was evaluated. The micelles loaded with TCN are bactericidal; bacteria are killed in less than two minutes of exposure. The most likely interpretation of the data is that the biocide is transferred to the bacteria by repeated micelle/bacteria contacts, and not via the solution. PMID:21275041

  2. Dynamic thermal field-induced gradient soft-shear for highly oriented block copolymer thin films.

    PubMed

    Singh, Gurpreet; Yager, Kevin G; Berry, Brian; Kim, Ho-Cheol; Karim, Alamgir

    2012-11-27

    As demand for smaller, more powerful, and energy-efficient devices continues, conventional patterning technologies are pushing up against fundamental limits. Block copolymers (BCPs) are considered prime candidates for a potential solution via directed self-assembly of nanostructures. We introduce here a facile directed self-assembly method to rapidly fabricate unidirectionally aligned BCP nanopatterns at large scale, on rigid or flexible template-free substrates via a thermally induced dynamic gradient soft-shear field. A localized differential thermal expansion at the interface between a BCP film and a confining polydimethylsiloxane (PDMS) layer due to a dynamic thermal field imposes the gradient soft-shear field. PDMS undergoes directional expansion (along the annealing direction) in the heating zone and contracts back in the cooling zone, thus setting up a single cycle of oscillatory shear (maximum lateral shear stress ∼12 × 10(4) Pa) in the system. We successfully apply this process to create unidirectional alignment of BCP thin films over a wide range of thicknesses (nm to μm) and processing speeds (μm/s to mm/s) using both a flat and patterned PDMS layer. Grazing incidence small-angle X-ray scattering measurements show absolutely no sign of isotropic population and reveal ≥99% aligned orientational order with an angular spread Δθ(fwhm) ≤ 5° (full width at half-maximum). This method may pave the way to practical industrial use of hierarchically patterned BCP nanostructures. PMID:23106286

  3. On the self-assembly of brush block copolymers in thin films.

    PubMed

    Hong, Sung Woo; Gu, Weiyin; Huh, June; Sveinbjornsson, Benjamin R; Jeong, Gajin; Grubbs, Robert Howard; Russell, Thomas P

    2013-11-26

    We describe a simple route to fabricate two dimensionally well-ordered, periodic nanopatterns using the self-assembly of brush block copolymers (brush BCPs). Well-developed lamellar microdomains oriented perpendicular to the substrate are achieved, without modification of the underlying substrates, and structures with feature sizes greater than 200 nm are generated due to the reduced degree of chain entanglements of brush BCPs. A near-perfect linear scaling law was found for the period, L, as a function of backbone degree of polymerization (DP) for two series of brush BCPs. The exponent increases slightly from 0.99 to 1.03 as the side chain molecular weight increases from ∼2.4 to ∼4.5 kg/mol(-1) and saturated with further increase in the side chain molecular weight due to the entropic penalty associated with the packing of the side chains. Porous templates and scaffolds from brush BCP thin films are also obtained by selective etching of one component. PMID:24156297

  4. Controlling Directed Self-Assembly and Sintering of Gold Nanorods in Patterned Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Lai, Fengyuan

    As the miniaturization of electronic devices continues, proper thermal management is crucial to ensure the optimum performance and reliability of such devices within their specification. Of primary interest are the so-called thermal interface materials to minimize the thermal resistance between the heat source and the heat sink. To this end, polymer nanocomposites composed of a polymer matrix and nanoscale fillers with high thermal conductivity have attracted tremendous attention. It has been demonstrated that the formation of a nanoparticle assembly inside the polymer matrix provides a continuous pathway for efficient heat transfer, and thus it is essential for achieving high thermal conductivity. In this work, we explored the ability to direct the self-assembly of gold nanorods (AuNRs) via patterned block copolymer (BCP) thin films. Selective sequestration of AuNRs with various aspect ratios in one block domain was achieved, with over 30% of the surface covered by an ordered AuNR assembly orienting parallel to the geometric confinement. The final nanostructure resulting from the directed self-assembly process is determined by the competition between thermodynamic consideration and kinetic factors. The coalescence and sintering of the AuNR assembly was accomplished by both furnace thermal annealing and rapid thermal annealing at low temperatures. The mechanism through which efficient sintering occurred is investigated with scanning electron microscopy. It is found that the sintering process initially takes place locally, resulting in small AuNR aggregates. Eventually the aggregates grow into a globally continuous, percolating network structure. In addition, the overall heat transfer coefficient was measured in an environmental scanning electron microscope by following droplet growth over time. The present study opens up new opportunities to accomplish controlled assembly of nanoparticles with high concentration for different nanorod-based applications as well as

  5. Block copolymer battery separator

    DOEpatents

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  6. Directed Assembly of Lamellae Forming Block Copolymer Thin Films near the Order-Disorder Transition

    SciTech Connect

    Kim, Sangwon; Nealey, Paul F.; Bates, Frank S.

    2014-08-07

    The impact of thin film confinement on the ordering of lamellae was investigated using symmetric poly(styrene-b-[isoprene-ran-epoxyisoprene]) diblock copolymers bound by nonpreferential wetting interfaces. The order–disorder transition temperature (TODT) and the occurrence of composition fluctuations in the disordered state are not significantly affected by two-dimensional confinement. Directed self-assembly using chemical patterning is demonstrated near TODT. These results establish the minimum feature size attainable using directed self-assembly of a given diblock copolymer system.

  7. New Poly(dimethylsiloxane)/Poly(perfluorooctylethyl acrylate) Block Copolymers: Structure and Order Across Multiple Length Scales in Thin Films

    SciTech Connect

    E Martinelli; G Galli; S Krishnan; M Paik; C Ober; D Fischer

    2011-12-31

    Three sets of a new class of low surface tension block copolymers were synthesized consisting of a poly(dimethylsiloxane) (PDMS) block and a poly(perfluorooctylethyl acrylate) (AF8) block. The polymers were prepared using a bromo-terminated PDMS macroinitiator, to which was attached an AF8 block grown using atom transfer radical polymerization (ATRP) in such a designed way that the molecular weight and composition of the two polymer blocks were regularly varied. The interplay of both the phase separated microstructure and the mesomorphic character of the fluorinated domains with their effect on surface structure was evaluated using a suite of analytical tools. Surfaces of spin-coated and thermally annealed films were assessed using a combination of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) studies. Both atomic force microscopy (AFM) measurements and grazing incidence small angle X-ray scattering (GISAXS) studies were carried out to evaluate the microstructure of the thin films. Even in block copolymers in which the PDMS block was the majority component, a significant presence of the lower surface energy AF8 block was detected at the film surface. Moreover, the perfluorooctyl helices of the AF8 repeat units were highly oriented at the surface in an ordered, tilted smectic structure, which was compared with those of the bulk powder samples using wide-angle X-ray powder diffraction (WAXD) studies.

  8. Deconvoluting the mechanism of microwave annealing of block copolymer thin films.

    PubMed

    Jin, Cong; Murphy, Jeffrey N; Harris, Kenneth D; Buriak, Jillian M

    2014-04-22

    The self-assembly of block copolymer (BCP) thin films is a versatile method for producing periodic nanoscale patterns with a variety of shapes. The key to attaining a desired pattern or structure is the annealing step undertaken to facilitate the reorganization of nanoscale phase-segregated domains of the BCP on a surface. Annealing BCPs on silicon substrates using a microwave oven has been shown to be very fast (seconds to minutes), both with and without contributions from solvent vapor. The mechanism of the microwave annealing process remains, however, unclear. This work endeavors to uncover the key steps that take place during microwave annealing, which enable the self-assembly process to proceed. Through the use of in situ temperature monitoring with a fiber optic temperature probe in direct contact with the sample, we have demonstrated that the silicon substrate on which the BCP film is cast is the dominant source of heating if the doping of the silicon wafer is sufficiently low. Surface temperatures as high as 240 °C are reached in under 1 min for lightly doped, high resistivity silicon wafers (n- or p-type). The influence of doping, sample size, and BCP composition was analyzed to rule out other possible mechanisms. In situ temperature monitoring of various polymer samples (PS, P2VP, PMMA, and the BCPs used here) showed that the polymers do not heat to any significant extent on their own with microwave irradiation of this frequency (2.45 GHz) and power (∼600 W). It was demonstrated that BCP annealing can be effectively carried out in 60 s on non-microwave-responsive substrates, such as highly doped silicon, indium tin oxide (ITO)-coated glass, glass, and Kapton, by placing a piece of high resistivity silicon wafer in contact with the sample-in this configuration, the silicon wafer is termed the heating element. Annealing and self-assembly of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and polystyrene-block-poly(methyl methacrylate) (PS

  9. Azobenzene photoswitching as a tool for controlling block copolymer self-assembly in dip-coated thin films

    NASA Astrophysics Data System (ADS)

    Vapaavuori, Jaana; Grosrenaud, Josué; Borozenko, Kateryna; Pellerin, Christian; Bazuin, Geraldine; Department of Chemistry, University of Montreal Team

    Understanding how to control the characteristics of microphase-separated block copolymer thin films is of crucial importance for developing nanotechnological applications, such as producing nanoscale lithography templates for the electronics industry. The supramolecular complexation of small molecules selectively to one of the blocks in suitable block copolymers enables modulating the block volume fractions and thereby controlling the type of surface morphology obtained in thin films. In this contribution, we show that the morphology of dip-coated polystyrene-b-poly(4-vinylpyridine) polymer films containing a hydrogen-bonding azobenzene guest can be further controlled using light as an external in situ stimulus during the dip-coating procedure. A change from spherical to cylindrical morphology was demonstrated when the geometry of the azobenzene units was switched by illumination at 365 nm. Film thickness measurements revealed that the thickness of the films can also be tailored by light, since films prepared under irradiation are significantly thicker than non-irradiated ones. The photochemical requirements to guide the choice of azobenzene molecule and the nature of the solvent used will be discussed in view of an optimal material combination for easily directable systems.

  10. Shear alignment and realignment of sphere-forming and cylinder-forming block-copolymer thin films

    NASA Astrophysics Data System (ADS)

    Marencic, Andrew P.; Adamson, Douglas H.; Chaikin, Paul M.; Register, Richard A.

    2010-01-01

    In common with many other structured fluids, block copolymers can be effectively oriented by shear. This susceptibility to shear alignment has previously been shown to hold even in thin films, containing as few as two layers of spherical microdomains, or even a single layer of cylindrical microdomains. A phenomenological model has been proposed [M. W. Wu, R. A. Register, and P. M. Chaikin, Phys. Rev. E 74, 040801(R) (2006)] to describe the alignment of such block-copolymer films, yielding the microdomain lattice order parameter as a function of shearing temperature, stress, and time. Here we directly test the central idea of that model, that the grains which are most misaligned with the shear direction are selectively destroyed, to reform in a direction more closely aligned with the shear. Films are first shear aligned from a polygrain state into a monodomain orientation and are then subjected to a second shear, at a variable stress (σ) and misorientation angle (δθ) relative to the monodomain director, allowing the effects of σ and δθ to be independently and systematically probed. For both cylinder-forming and sphere-forming block copolymers, these experiments confirm the basic premise of the model, as the stress required for realignment increases monotonically as δθ becomes smaller. For a cylinder-forming block copolymer, we find that the characteristic stress σc required to realign cylinders from one monodomain orientation to another is indistinguishable from that required to generate a monodomain orientation from the polygrain state. By contrast, the hexagonal lattice of spheres requires a value of σc more than 3 times as high for reorientation than for generation of the initial monodomain orientation.

  11. Analysis of Order Formation in Block Copolymer Thin Films UsingResonant Soft X-Ray Scattering

    SciTech Connect

    Virgili, Justin M.; Tao, Yuefei; Kortright, Jeffrey B.; Balsara,Nitash P.; Segalman, Rachel A.

    2006-11-27

    The lateral order of poly(styrene-block-isoprene) copolymer(PS-b-PI) thin films is characterized by the emerging technique ofresonant soft X-ray scattering (RSOXS) at the carbon K edge and comparedto ordering in bulk samples of the same materials measured usingconventional small-angle X-ray scattering. We show resonance using theoryand experiment that the loss of scattering intensity expected with adecrease in sample volume in the case of thin films can be overcome bytuning X-rays to the pi* resonance of PS or PI. Using RSOXS, we study themicrophase ordering of cylinder- and phere-forming PS-b-PI thin films andcompare these results to position space data obtained by atomic forcemicroscopy. Our ability to examine large sample areas (~;9000 mu m2) byRSOXS enables unambiguous identification of the lateral lattice structurein the thin films. In the case of the sphere-forming copolymer thin film,where the spheres are hexagonally arranged, the average sphere-to-spherespacing is between the bulk (body-centered cubic) nearest neighbor andbulk unit cell spacings. In the case of the cylinder-forming copolymerthin film, the cylinder-to-cylinder spacing is within experimental errorof that obtained in the bulk.

  12. Interfaces between Block Copolymer Domains

    NASA Astrophysics Data System (ADS)

    Kim, Jaeup; Jeong, Seong-Jun; Kim, Sang Ouk

    2011-03-01

    Block copolymers naturally form nanometer scale structures which repeat their geometry on a larger scale. Such a small scale periodic pattern can be used for various applications such as storage media, nano-circuits and optical filters. However, perfect alignment of block copolymer domains in the macroscopic scale is still a distant dream. The nanostructure formation usually occurs with spontaneously broken symmetry; hence it is easily infected by topological defects which sneak in due to entropic fluctuation and incomplete annealing. Careful annealing can gradually reduce the number of defects, but once kinetically trapped, it is extremely difficult to remove all the defects. One of the main reasons is that the defect finds a locally metastable morphology whose potential depth is large enough to prohibit further morphology evolution. In this work, the domain boundaries between differently oriented lamellar structures in thin film are studied. For the first time, it became possible to quantitatively study the block copolymer morphology in the transitional region, and it was shown that the twisted grain boundary is energetically favorable compared to the T-junction grain boundary. [Nano Letters, 9, 2300 (2010)]. This theoretical method successfully explained the experimental results.

  13. Block copolymer investigations

    NASA Astrophysics Data System (ADS)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  14. Neutral wetting brush layers for block copolymer thin films using homopolymer blends

    NASA Astrophysics Data System (ADS)

    Antonioli, Diego; Sparnacci, Katia; Laus, Michele; Lupi, Federico Ferrarese; Giammaria, Tommaso Jacopo; Seguini, Gabriele; Ceresoli, Monica; Perego, Michele; Gianotti, Valentina

    2016-05-01

    Binary homopolymer blends of two hydroxyl-terminated polystyrene (PS-OH) and polymethylmethacrylate (PMMA-OH) homopolymers (Mn ~ 16000 g mol-1) were grafted on SiO2 substrates by high-temperature (T > 150 °C), short-time (t < 600 s) thermal treatments. The resulting brush layer was tested to screen preferential interactions of the SiO2 substrate with the different symmetric and asymmetric PS-b-PMMA block copolymers deposited on top of the grafted molecules. By properly adjusting the blend composition and the processing parameters, an efficient surface neutralization path was identified, enabling the formation, in the block copolymer film, of homogeneous textures of lamellae or cylinders perpendicularly oriented with respect to the substrate. A critical interplay between the phase segregation of the homopolymer blends and their grafting process on the SiO2 was observed. In fact, the polar SiO2 is preferential for the PMMA-rich phase that forms a homogeneous layer on the substrate, while the PS-rich phase is located at the polymer-air interface. During the thermal treatment, phase segregation and grafting proceed simultaneously. Complete wetting of the PS rich phase on the PMMA rich phase leads to the formation of a PS/PMMA bilayer. In this case, the progressive diffusion of PS chains toward the polymer-SiO2 interface during the thermal treatment allows tuning of the brush layer composition

  15. Neutral wetting brush layers for block copolymer thin films using homopolymer blends processed at high temperatures

    NASA Astrophysics Data System (ADS)

    Ceresoli, M.; Palermo, M.; Ferrarese Lupi, F.; Seguini, G.; Perego, M.; Zuccheri, G.; Phadatare, S. D.; Antonioli, D.; Gianotti, V.; Sparnacci, K.; Laus, M.

    2015-10-01

    Binary homopolymer blends of two hydroxyl-terminated polystyrene (PS-OH) and polymethylmethacrylate (PMMA-OH) homopolymers (Mn ˜ 16000 g mol-1) were grafted on SiO2 substrates by high-temperature (T > 150 °C), short-time (t < 600 s) thermal treatments. The resulting brush layer was tested to screen preferential interactions of the SiO2 substrate with the different symmetric and asymmetric PS-b-PMMA block copolymers deposited on top of the grafted molecules. By properly adjusting the blend composition and the processing parameters, an efficient surface neutralization path was identified, enabling the formation, in the block copolymer film, of homogeneous textures of lamellae or cylinders perpendicularly oriented with respect to the substrate. A critical interplay between the phase segregation of the homopolymer blends and their grafting process on the SiO2 was observed. In fact, the polar SiO2 is preferential for the PMMA-rich phase that forms a homogeneous layer on the substrate, while the PS-rich phase is located at the polymer-air interface. During the thermal treatment, phase segregation and grafting proceed simultaneously. Complete wetting of the PS rich phase on the PMMA rich phase leads to the formation of a PS/PMMA bilayer. In this case, the progressive diffusion of PS chains toward the polymer-SiO2 interface during the thermal treatment allows tuning of the brush layer composition.

  16. Simulations on a swollen gyroid nanostructure in thin films relevant to systems of ionic block copolymers.

    PubMed

    Knychała, P; Banaszak, M

    2014-07-01

    Self-assembly of symmetric A/S-B copolymer melt to gyroid nanostructure, partitioning space into interpenetrating nano-labyrinths (channels), in thin films, is investigated using a minimal lattice model with short-range interactions. This model is relevant to poly(styrenesulfonate)-b -polymethylbutylene melt consisting of three types of segments, A, B and S, corresponding to styrene, methylbutylene and styrenesulfonate, respectively. A single sequence of A, B, and S is used in simulations and the fraction of S segments is fixed at p = 0.647 which corresponds to experimental data. The film thickness, L(z), is restricted to nine values (L(z) = 17 , 22, 26, 30, 34, 42, 51, 60, and 68 in units of the underlying lattice constant). The gyroid nanostructure is found to be stable if the film thickness is equal to or greater than the bulk period of the nanophase. The observed gyroid is referred to as swollen since the volume fraction of two continuous networks made of the B segments is anomalous with respect to that of conventional diblock copolymers. In contrast to bulk state, we do not directly observe the order-disorder transition to the gyroid nanophase for thin films. In this case, however, simulations indicate a direct order-disorder transition to a lamellar phase and the order-disorder transition temperature is higher than that in the bulk state, varying strongly with the film thickness. PMID:25080175

  17. Surface Morphology Diagram for Cylinder-Forming Block Copolymer Thin Films

    SciTech Connect

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

    2008-01-01

    We investigate the effect of annealing temperature (T), film thickness (hf) on the surface morphology of flow coated films of a cylinder forming block copolymer, poly (styrene-block-methyl methacrylate) (PS-b-PMMA). Surface morphology transitions from a perpendicular to a parallel cylinder orientation with respect to the substrate with increasing hf are observed in these model frustrated-interaction films where the substrate interaction is preferential for one of the blocks (PMMA) and nearly neutral for the other interface (polymer-air). In these films a transition occurs from cylinders oriented parallel to the substrate to a mixed or hybrid state where the two orientations coexist followed by a transition to cylinders oriented perpendicularly to the polymer-air interface for larger hf. The characteristic values of hf defining these surface morphological transitions depend on T and we construct a surface morphology diagram as a function of hf and T. The surface morphology diagram is found to depend on the method of film formation (flow coated versus spun cast films) so non-equilibrium effects evidently have a large effect on the surface pattern morphology. In particular, the residual solvent within the film (quantified by neutron reflectivity measurements) in the context of physics of glass-formation can have a large effect on the surface morphology diagram.

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

    PubMed Central

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

    2009-01-01

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

  19. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

    NASA Astrophysics Data System (ADS)

    Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; Sweat, Daniel P.; Wang, Xudong; Gopalan, Padma

    2016-06-01

    In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and

  20. Processing Cyclic Peptide-polymer Conjugates in Block Copolymer Thin Films for Sub-nm Porous Membranes

    NASA Astrophysics Data System (ADS)

    Zhang, Chen; Xu, Ting

    2014-03-01

    Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation. Inspired by natural protein channels, we have developed an approach using cyclic peptide nanotubes (CPNs) embedded in polymeric matrix to mimic the transport of natural channels. The co-assembly of polymer-covered CPNs in a block copolymer (BCP) thin film requires the synchronization of two self-assembly processes, namely the microphase separation of BCP and the nanotube growth of CP-polymer conjugates. We systematically investigated the co-assembly of isolated CP-poly(ethylene glycol) (CP-PEG) conjugates and polystyrene-b-poly (methyl methacrylate) (PS-b-PMMA) in thin films as a function of CP-PEG loading (fCP-PEG) and solvent-polymer interactions. We find that there is a strong dependence of the co-assembly process on fCP-PEG due to thermodynamic limit of incorporating one CPN in one PMMA microdomain, as well as the kinetic pathway in which favorable PEG-solvent interaction helps to disperse CPNs and thus lowers the activation energy barrier of the system. This study presents critical insights in guided assemblies of functional building blocks within nanoscopic frameworks. DOE-EFRC-Gas Separation, Army Research Office.

  1. Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer.

    PubMed

    Zhang, Jieqian; Clark, Michael B; Wu, Chunyi; Li, Mingqi; Trefonas, Peter; Hustad, Phillip D

    2016-01-13

    Directed self-assembly (DSA) of block copolymers (BCPs) is an attractive advanced patterning technology being considered for future integrated circuit manufacturing. By controlling interfacial interactions, self-assembled microdomains in thin films of polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, can be oriented perpendicular to surfaces to form line/space or hole patterns. However, its relatively weak Flory interaction parameter, χ, limits its capability to pattern sub-10 nm features. Many BCPs with higher interaction parameters are capable of forming smaller features, but these "high-χ" BCPs typically have an imbalance in surface energy between the respective blocks that make it difficult to achieve the required perpendicular orientation. To address this challenge, we devised a polymeric surface active additive mixed into the BCP solution, referred to as an embedded neutral layer (ENL), which segregates to the top of the BCP film during casting and annealing and balances the surface tensions at the top of the thin film. The additive comprises a second BCP with a "neutral block" designed to provide matched surface tensions with the respective polymers of the main BCP and a "surface anchoring block" with very low surface energy that drives the material to the air interface during spin-casting and annealing. The surface anchoring block allows the film to be annealed above the glass transition temperature of the two materials without intermixing of the two components. DSA was also demonstrated with this embedded neutral top layer formulation on a chemical patterned template using a single step coat and simple thermal annealing. This ENL technology holds promise to enable the use of high-χ BCPs in advanced patterning applications. PMID:26682931

  2. Block copolymer nanolithography for the fabrication of patterned media.

    SciTech Connect

    Warke, Vishal V; Bakker, Martin G; Hong, Kunlun; Mays, Jimmy; Britt, Phillip F; Li, Xuefa; Wang, Jin

    2008-01-01

    Abstract Bit patterned perpendicular media has the potential to increase the density of magnetic recording beyond what can be achieved by granular media. Self assembling diblock copolymers are of interest as templates for patterned media, as they potentially provide a low cost fabrication route. A method to fabricate the desired pattern using cylinder forming diblock copolymers of (PS-b-PMMA) as template is reported. Upon phase separation hexagonally packed cylinders of the minority phase (PMMA) surrounded by the continuous majority phase (PS) are obtained. The processing sequence began with spin coating the block copolymer on a suitable substrate, followed by annealing the block copolymer thin film in vacuum to orient it perpendicular to the substrate. Block copolymer templates were obtained by glacial acetic acid treatment which opened the pores in the block copolymer thin film. Ni was electrodeposited in the block copolymer templates and this pattern was then transferred onto the underlying substrate by ion milling

  3. Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application.

    PubMed

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

    2016-07-01

    Block copolymers (BCPs) and their directed self-assembly (DSA) has emerged as a realizable complementary tool to aid optical patterning of device elements for future integrated circuit advancements. Methods to enhance BCP etch contrast for DSA application and further potential applications of inorganic nanomaterial features (e.g., semiconductor, dielectric, metal and metal oxide) are examined. Strategies to modify, infiltrate and controllably deposit inorganic materials by utilizing neat self-assembled BCP thin films open a rich design space to fabricate functional features in the nanoscale regime. An understanding and overview on innovative ways for the selective inclusion/infiltration or deposition of inorganic moieties in microphase separated BCP nanopatterns is provided. Early initial inclusion methods in the field and exciting contemporary reports to further augment etch contrast in BCPs for pattern transfer application are described. Specifically, the use of evaporation and sputtering methods, atomic layer deposition, sequential infiltration synthesis, metal-salt inclusion and aqueous metal reduction methodologies forming isolated nanofeatures are highlighted in di-BCP systems. Functionalities and newly reported uses for electronic and non-electronic technologies based on the inherent properties of incorporated inorganic nanostructures using di-BCP templates are highlighted. We outline the potential for extension of incorporation methods to triblock copolymer features for more diverse applications. Challenges and emerging areas of interest for inorganic infiltration of BCPs are also discussed. PMID:26749571

  4. Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors.

    PubMed

    Choi, Jonathan W; Li, Zhaodong; Black, Charles T; Sweat, Daniel P; Wang, Xudong; Gopalan, Padma

    2016-06-01

    In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes. PMID:27216015

  5. Crystalline Structure in Thin Films of DEH-PPV Homopolymer And PPV-B-PI Rod-Coil Block Copolymers

    SciTech Connect

    Olsen, B.D.; Alcazar, D.; Krikorian, V.; Toney, M.F.; Thomas, E.L.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley /MIT /SLAC, SSRL

    2009-04-30

    The rod orientation and crystalline packing of a model semiconducting rodlike polymer, poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene) (DEH-PPV), is shown to affect the self-assembly of weakly segregated rod-coil block copolymers. The in-plane packing of DEH-PPV rods in lamellar poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene-b-isoprene) (DEH-PPV-b-PI) diblock copolymers is nearly identical to that observed in DEH-PPV homopolymers for compositions ranging from 0.42 to 0.82 vol % coil block. The crystal structure of DEH-PPV, characterized by grazing incidence X-ray diffraction and electron diffraction, consists of a tetragonal unit cell having c = 0.665 nm with a = b = 1.348 nm. The polymer chain axis is aligned along the [001] direction, and the nearest neighbor rod-rod spacing along 110 is 1.0 nm. As-cast thin films of DEH-PPV homopolymer demonstrate chain alignment primarily perpendicular to the substrate in 5100 g/mol homopolymer, while for 3500 g/mol homopolymer the chains align both perpendicular and parallel to the substrate. For the DEH-PPV-b-PI block copolymers, a sharper 001 reflection is observed due to the effect of microphase separation, improving alignment and stacking of the rods. The lamellar phases have a smectic A-like packing structure with the rods oriented parallel to the lamellar normal regardless of coil fraction; however, at coil fractions above about 0.8 the crystalline lattice of the rods becomes rapidly disordered as evidenced by loss of all but the two strongest Bragg reflections. This suggests that the constraints of packing into the unit cell outweigh the chain stretching and segment-segment repulsion energies that are predicted to lead to a transition from normal (smectic A) to tilted (smectic C) rod orientation within the lamellae at high coil fraction; increasing coil fraction breaks apart the crystalline lattice rather than distorting it into a tilted polymorph.

  6. Skin delivery by block copolymer nanoparticles (block copolymer micelles).

    PubMed

    Laredj-Bourezg, Faiza; Bolzinger, Marie-Alexandrine; Pelletier, Jocelyne; Valour, Jean-Pierre; Rovère, Marie-Rose; Smatti, Batoule; Chevalier, Yves

    2015-12-30

    Block copolymer nanoparticles often referred to as "block copolymer micelles" have been assessed as carriers for skin delivery of hydrophobic drugs. Such carriers are based on organic biocompatible and biodegradable materials loaded with hydrophobic drugs: poly(lactide)-block-poly(ethylene glycol) copolymer (PLA-b-PEG) nanoparticles that have a solid hydrophobic core made of glassy poly(d,l-lactide), and poly(caprolactone)-block-poly(ethylene glycol) copolymer (PCL-b-PEG) nanoparticles having a liquid core of polycaprolactone. In vitro skin absorption of all-trans retinol showed a large accumulation of retinol in stratum corneum from both block copolymer nanoparticles, higher by a factor 20 than Polysorbate 80 surfactant micelles and by a factor 80 than oil solution. Additionally, skin absorption from PLA-b-PEG nanoparticles was higher by one order of magnitude than PCL-b-PEG, although their sizes (65nm) and external surface (water-swollen PEG layer) were identical as revealed by detailed structural characterizations. Fluorescence microscopy of histological skin sections provided a non-destructive picture of the storage of Nile Red inside stratum corneum, epidermis and dermis. Though particle cores had a different physical states (solid or liquid as measured by (1)H NMR), the ability of nanoparticles for solubilization of the drug assessed from their Hildebrand solubility parameters appeared the parameter of best relevance regarding skin absorption. PMID:26602293

  7. Micrometer-Scale Ordering of Silicon-Containing Block Copolymer Thin Films via High-Temperature Thermal Treatments.

    PubMed

    Giammaria, Tommaso Jacopo; Ferrarese Lupi, Federico; Seguini, Gabriele; Perego, Michele; Vita, Francesco; Francescangeli, Oriano; Wenning, Brandon; Ober, Christopher K; Sparnacci, Katia; Antonioli, Diego; Gianotti, Valentina; Laus, Michele

    2016-04-20

    Block copolymer (BCP) self-assembly is expected to complement conventional optical lithography for the fabrication of next-generation microelectronic devices. In this regard, silicon-containing BCPs with a high Flory-Huggins interaction parameter (χ) are extremely appealing because they form high-resolution nanostructures with characteristic dimensions below 10 nm. However, due to their slow self-assembly kinetics and low thermal stability, these silicon-containing high-χ BCPs are usually processed by solvent vapor annealing or in solvent-rich ambient at a low annealing temperature, significantly increasing the complexity of the facilities and of the procedures. In this work, the self-assembly of cylinder-forming polystyrene-block-poly(dimethylsiloxane-random-vinylmethylsiloxane) (PS-b-P(DMS-r-VMS)) BCP on flat substrates is promoted by means of a simple thermal treatment at high temperatures. Homogeneous PS-b-P(DMS-r-VMS) thin films covering the entire sample surface are obtained without any evidence of dewetting phenomena. The BCP arranges in a single layer of cylindrical P(DMS-r-VMS) nanostructures parallel-oriented with respect to the substrate. By properly adjusting the surface functionalization, the heating rate, the annealing temperature, and the processing time, one can obtain correlation length values larger than 1 μm in a time scale fully compatible with the stringent requirements of the microelectronic industry. PMID:27020526

  8. Effect of χN and underlayer composition on self-assembly of thin films of block copolymers with energy asymmetric block

    NASA Astrophysics Data System (ADS)

    Lawson, Richard A.; Peters, Andrew J.; Nation, Benjamin D.; Ludovice, Peter J.; Henderson, Clifford L.

    2015-03-01

    Many high χ block copolymer (BCP) systems often have one block which shows a strong preference to wet the free interface at the top of the film. This property makes it difficult to form vertically aligned lamellae which are desired for many directed self-assembly (DSA) applications. To better understand this behavior, simulations of thin films of BCPs were carried out using a coarse-grained molecular dynamics (MD) model. The property that leads one block to preferentially wet the free interface over the other is a difference in cohesive energy density (CED) between the two blocks. Our simulation allows for the systematic variation in the CED of each block to investigate how the magnitude of these differences affects self-assembly behavior. BCPs with no CED differences between the blocks show large ranges of underlayer compositions where vertical lamellae will form that are minimally affected by changing χ of the BCP. The range where vertical lamellae will form can be thought of as a process window. Increasing the CED asymmetry of the BCP (i.e. the difference in CED between blocks) causes a reduction in the process window and also causes a shift in the underlayer composition that is the center of the window. Increasing χ increases the process window for vertical lamellae in CED asymmetric systems. This behavior is determined by the trade-off in energy due to three interfacial interactions: A-B interface, film-free surface interface, and film-underlayer interface. At the limits of very high CED asymmetry and low χ, there may be no underlayer compositions where vertical lamellae will form. A simplified model was also developed that can accurately predict these process windows for different CED asymmetry and χ values on the order of seconds and minutes compared to hours and days for the full simulation.

  9. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G.; Matzger, Adam J.; Benin, Annabelle I.; Willis, Richard R.

    2012-12-04

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  10. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2012-11-13

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  11. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2014-11-11

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

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

    PubMed

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

    2016-03-30

    Solvothermal vapor annealing (STVA) was employed to induce microphase separation in a lamellar forming block copolymer (BCP) thin film containing a readily degradable block. Directed self-assembly of poly(styrene)-block-poly(d,l-lactide) (PS-b-PLA) BCP films using topographically patterned silicon nitride was demonstrated with alignment over macroscopic areas. Interestingly, we observed lamellar patterns aligned parallel as well as perpendicular (perpendicular microdomains to substrate in both cases) to the topography of the graphoepitaxial guiding patterns. PS-b-PLA BCP microphase separated with a high degree of order in an atmosphere of tetrahydrofuran (THF) at an elevated vapor pressure (at approximately 40-60 °C). Grazing incidence small-angle X-ray scattering (GISAXS) measurements of PS-b-PLA films reveal the through-film uniformity of perpendicular microdomains after STVA. Perpendicular lamellar orientation was observed on both hydrophilic and relatively hydrophobic surfaces with a domain spacing (L0) of ∼32.5 nm. The rapid removal of the PLA microdomains is demonstrated using a mild basic solution for the development of a well-defined PS mask template. GISAXS data reveal the through-film uniformity is retained following wet etching. The experimental results in this article demonstrate highly oriented PS-b-PLA microdomains after a short annealing period and facile PLA removal to form porous on-chip etch masks for nanolithography application. PMID:26950246

  13. Influence of Interfacial Energy on Electric-Field-Induced Sphere-to-Cylinder Transition in Block Copolymer Thin Films

    SciTech Connect

    Wang, J.; Chen, W; Russell, T

    2008-01-01

    The effect of the interfacial energy on the electric-field-induced sphere-to-cylinder (S-to-C) transition in polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) copolymer thin films was studied as a function of the difference in the interfacial interactions of the PS and PMMA blocks with the substrate, d. It was found that the interfacial energies altered both the critical electric field strength and the time scales of kinetics. A very strong preferential interfacial interaction suppressed the electric-field-induced S-to-C transition even though such a transition occurred on a neutralized surface where the interfacial interactions were balanced. For a moderate interfacial interaction, the S-to-C transition can be induced by an applied electric field, but the time scale of the morphology change is much longer. Furthermore, the formation of ionic complexes in the BCP was found to enhance the electric-field-induced S-to-C transition even on a native Si substrate without any surface modification, providing a simple route to generate ordered arrays of high-aspect-ratio cylinders oriented normal to a film surface.

  14. An in-situ study of structure evolution in block copolymer thin films of PS-PEO during solvent vapor annealing

    NASA Astrophysics Data System (ADS)

    Mokarian-Tabari, Parvaneh; Collins, Timothy W.; Morris, Michael A.

    2010-03-01

    Thin films of block copolymers are promising candidates for producing nano scale structures in the electronic industry such as sub-30 nm templates for nanolithography [1]. To be able to produce structures with desired morphologies and minimum defects, it is important to have a deep understanding of the ordering mechanism. We have carried out a systematic study on spin cast films made of poly(styrene-b-ethylene oxide) block copolymers during solvent and thermal annealing. The swelling behavior of the films were studied by using an environmental cell to control the vapor pressure of the gas and equipped with small angle light scattering apparatus. Our results show that the swelling starts within seconds of exposure to toluene vapor and the domains form within minutes. Cyclic transition between perpendicular and horizontal arrays is observed. [1] Ruiz R, Kang H M, Detcheverry F A, Dobisz E, Kercher D S, Albrecht T R, de Pablo J J and Nealey P F, 2008, 321, 936

  15. Structure Formation of Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Abetz, Volker

    2013-03-01

    Isoporous membranes have received increasing attention during the last couple of years. The advantage of these materials is to give access to membranes with a very high number density of pores with controlled diameters, thus leading to ultrafiltration membranes with a very high permeability, and simultaneously also with a very high selectivity in terms of size exclusion. Different approaches have been reported, which typically involve the transfer of a thin block copolymer film from a solid to a porous support, eventually followed by an edging step. An alternative strategy is to form integral asymmetric membranes, where the thin top layer is continuously changing into a spongy support layer, thus avoiding the build-up of mechanical stresses. This happens by subjecting the cast polymer solution film into a precipitant, inducing the so-called phase inversion by exchange of solvent with the non-solvent. Here it is important to have a system where solvent and nonsolvent are fully miscible. This strategy also enables the direct formation of open pores without a subsequent edging step, if the solvents and nonsolvents are appropriately chosen. Different types of amphiphilic block copolymers based on styrene, 2- or 4-vinyl pyridine, and ethylene oxide with various compositions and molecular weights will be discussed. These block copolymers were dissolved at different concentrations in various solvent mixtures, and then cast on a non-woven support, which was either pretreated with a liquid, or not. Varying the time before the cast solution was subjected to phase inversion, as well as choosing the temperature of the precipitation bath, are further parameters having strong influence on the obtained membrane film structure. Membranes with pore forming blocks showing pH or temperature sensitive behaviour can be reversibly switched from an open state to a closed state. The size of the pores can be controlled by both molecular weight and composition of the block copolymers.

  16. Materials Design for Block Copolymer Lithography

    NASA Astrophysics Data System (ADS)

    Sweat, Daniel Patrick

    Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up

  17. Directed self-assembly of block copolymer thin films: From fundamentals science to applications

    NASA Astrophysics Data System (ADS)

    Teel, George Lewis

    A modern approach to satellite based experimentation has evolved from large, multi-instrumented satellites, to cheaper, smaller, almost disposable yet still reliable small spacecrafts. These small satellites are either sent to the International Space Station (ISS) to be dropped out into low earth orbit (LEO), or dropped off as a secondary payload into various orbits. While it is cheap to have small spacecraft accomplishing these missions, the lifetime expectancy is very short. Currently there are no commercialized propulsion systems that exist to keep them flying for prolonged periods of time. Recently researched at the Micro Propulsion and Nanotechnology Lab (MPNL), at the George Washington University (GWU), have been developments of a variety of Vacuum Arc Thrusters (VAT's) dubbed Micro-Cathode Vacuum Arc Thrusters (muCATs). muCAT's provide an inert electric means of propulsion for small spacecraft. The issue with these muCATs has been their efficiency levels and low amounts of thrust that they provide. The muCATs can provide muN levels of thrust per pulse. While being proficient for small spacecrafts, an increase in thrust is highly sought for, but the improvements must retain a small footprint and low power consumption. The topic of this thesis is the development and characterization of a new type of muCAT. The interest in this new design has been conceptualized based on experiments for plasma coating techniques. By utilizing the physics of evaporation, which has been used to decrease macroparticles (MP's) for thin film deposition, it has been theorized to also be applied to VAT technology. The concept is to increase levels of thrust with the muCAT, and provide higher levels of efficiency. This effect can be created without many additional components nor multiple additional loads to the thruster subsystem. Development of this new mechanic for thruster technology has been investigated through a variety of tests for fundamental proofs of concept. Running in two

  18. Block copolymer/ferroelectric nanoparticle nanocomposites

    NASA Astrophysics Data System (ADS)

    Pang, Xinchang; He, Yanjie; Jiang, Beibei; Iocozzia, James; Zhao, Lei; Guo, Hanzheng; Liu, Jin; Akinc, Mufit; Bowler, Nicola; Tan, Xiaoli; Lin, Zhiqun

    2013-08-01

    Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were first synthesized by exploiting amphiphilic unimolecular star-like poly(acrylic acid)-block-polystyrene (PAA-b-PS) diblock copolymers as nanoreactors. Subsequently, PS-functionalized BaTiO3 NPs were preferentially sequestered within PS nanocylinders in the linear cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer upon mixing the BaTiO3 NPs with PS-b-PMMA. The use of PS-b-PMMA diblock copolymers, rather than traditional homopolymers, offers the opportunity for controlling the spatial organization of PS-functionalized BaTiO3 NPs in the PS-b-PMMA/BaTiO3 NP nanocomposites. Selective solvent vapor annealing was utilized to control the nanodomain orientation in the nanocomposites. Vertically oriented PS nanocylinders containing PS-functionalized BaTiO3 NPs were yielded after exposing the PS-b-PMMA/BaTiO3 NP nanocomposite thin film to acetone vapor, which is a selective solvent for PMMA block. The dielectric properties of nanocomposites in the microwave frequency range were investigated. The molecular weight of PS-b-PMMA and the size of BaTiO3 NPs were found to exert an apparent influence on the dielectric properties of the resulting nanocomposites.Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were

  19. Use of combined chromatographic methods including thin-layer chromatography for analysis of complex polymer systems. Determination of the polydispersity of block copolymers of styrene and methyl methacrylate by gel permeation, thin-layer and pyrolysis gas chromatography.

    PubMed

    Belenkii, B G; Gankina, E S; Nefedov, P P; Lazareva, M A; Savitskaya, T S; Volchikhina, M D

    1975-05-01

    A combination of gel permeation chromatography (GPC), thin-layer chromatography (TLC) and pyrolysis gas chromatography (PGC) has been used for investigations of a polymethyl methacrylate-polystyrene-polymethyl methacrylate block copolymer. Continuous distribution of the polymer (40-mg sample) was attained according to the content of the styrene and methyl methacrylate units and of the block copolymer and according to the composition of the copolymer as functions of the hydrodynamic radius of the macromolecules. The polymer was subjected to a preliminary fractionation with an analytical gel chromatograph. The fractions were investigated by TLC, which permitted the separation of the block copolymer and the homopolymers. The composition of the fractions obtained by GPC and TLC was determined by PGC. As a result, it was possible to establish the composition of the block copolymer and its ratio to polymethyl methacrylate in each fraction. This investigation was based on a combination of highly effective fractionation by chromatographic methods with precise quantitative ratios obtained from Benoit's universal calibration graph and from determinations of the composition of the polymer fractions by PGC. The mechanism of the TLC of polymers, including the appearance of artefacts that distort the results of analysis, is also discussed. PMID:1150816

  20. On the mechanism of electrical conduction in thin films of some polysulfone-poly(alkylene oxide)-poly(dimethylsiloxane) block copolymers

    NASA Astrophysics Data System (ADS)

    Rusu, G. G.; Airinei, A.; Hamciuc, V.; Rambu, A. P.; Caplanus, I.; Rusu, G. I.

    2014-01-01

    Polysulfone poly(alkylene oxide)-poly(dimethylsiloxane) block copolymers have been prepared by the hydrosilylation reaction of allyl endcapped poly[(ethylene oxide) (propylene oxide)] oligomers with Si-H terminated polydimethylsiloxane in chlorobenzene using an isopropanol solution of hexachloroplatinic (IV) acid as catalyst for hydrosilylation. The temperature dependences of electrical conductivity and thermoelectric power (Seebeck coefficient) of copolymers were studied using thin-film samples deposited from dimethylformamide (spin coating technique) onto glass substrates. Organic films with reproducible electronic transport and optical properties can be obtained if, after deposition, they are submitted to a heat treatment consisting of several successive heating/cooling cycles within temperature range of (295-485) K. Investigated copolymers presents typical semiconducting characteristics. The values of some fundamental parameters (activation energy of electrical conduction, ratio of carrier mobilities, optical energy bandgap) have been determined. The mechanisms of electronic transport are identified in different temperature domains. Transmission and absorption spectra have been recorded and optical energy bandgaps are calculated from the absorption spectra. The thermistor effect of investigated copolymers is also discussed.

  1. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  2. Pattern transfer using block copolymers.

    PubMed

    Gu, Xiaodan; Gunkel, Ilja; Russell, Thomas P

    2013-10-13

    To meet the increasing demand for patterning smaller feature sizes, a lithography technique is required with the ability to pattern sub-20 nm features. While top-down photolithography is approaching its limit in the continued drive to meet Moore's law, the use of directed self-assembly (DSA) of block copolymers (BCPs) offers a promising route to meet this challenge in achieving nanometre feature sizes. Recent developments in BCP lithography and in the DSA of BCPs are reviewed. While tremendous advances have been made in this field, there are still hurdles that need to be overcome to realize the full potential of BCPs and their actual use. PMID:24000358

  3. Order-disorder transition in thin films of horizontally-oriented cylinder-forming block copolymers: thermal fluctuations vs. preferential wetting.

    PubMed

    Kim, Sangwon; Li, Wei; Fredrickson, Glenn H; Hawker, Craig J; Kramer, Edward J

    2016-07-01

    We present experimental and theoretical investigations of the order-disorder transition (ODT) in thin films of cylinder-forming diblock copolymers with asymmetric wetting conditions. Grazing incidence small-angle X-ray scattering (GISAXS) was implemented to determine the ODT temperatures (TODT) for poly(styrene-b-2-vinyl pyridine) (PS-P2VP) block copolymer thin films on a P2VP-preferential silicon substrate. Specifically, films consisting of multilayers of horizontally-oriented cylindrical structures (from 1- to 9-layers) were tested. We find that films with more than 2 cylindrical layers have a TODT comparable to the bulk case. However, TODT decreases as the film becomes thinner and the monolayer system has an ODT 30 °C below the bulk. Using self-consistent field theory (SCFT), we studied the ordering in corresponding thin films with asymmetric (top and bottom surface) wetting conditions. Surprisingly, SCFT is found to predict an opposite trend in TODT with film thickness than observed experimentally. Field-theoretic simulations with complex Langevin sampling were employed to resolve this discrepancy and demonstrate that thermal fluctuations in the PS-P2VP thin-film system dominate its ordering behavior in monolayer and bilayer films. PMID:27334558

  4. Block Copolymers with a Twist

    SciTech Connect

    Ho, R.; Chiang, Y; Chen, C; Wang, H; Hasegawa, H; Akasaka, S; Thomas, E; Burger, C; Hsiao, B

    2009-01-01

    Chiral block copolymers (BCPs*) comprising chiral entities were designed to fabricate helical architectures (i.e., twisted morphologies) from self-assembly. A new helical phase (H*) with P622 symmetry was discovered in the self-assembly of poly(styrene)-b-poly(l-lactide) (PS-PLLA) BCPs*. Hexagonally packed, interdigitated PLLA helical microdomains in a PS matrix were directly visualized by electron tomography. The phase diagram of the PS-PLLA BCPs* was also established. Phase transitions from the H* phase to the stable cylinder and gyroid phases were found after long-time annealing, suggesting that the H* is a long-lived metastable phase. In contrast to racemic poly(styrene)-b-poly(d,l-lactide) BCPs, chiral interaction significantly enhances the incompatibility between achiral PS and chiral PLLA blocks in the PS-PLLA BCPs* and can be estimated through the determination of the interaction parameter.

  5. Nanopatterned articles produced using surface-reconstructed block copolymer films

    DOEpatents

    Russell, Thomas P.; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2016-06-07

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  6. Method for making block siloxane copolymers

    DOEpatents

    Butler, Nora; Jessop, Edward S.; Kolb, John R.

    1982-01-01

    A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  7. Method for making block siloxane copolymers

    DOEpatents

    Butler, N.L.; Jessop, E.S.; Kolb, J.R.

    1981-02-25

    A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  8. Reordering transitions during annealing of block copolymer cylinder phases

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontal state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.

  9. Combining mixed titania morphologies into a complex assembly thin film by iterative block-copolymer-based sol-gel templating

    NASA Astrophysics Data System (ADS)

    Niedermeier, M. A.; Magerl, D.; Zhong, Q.; Nathan, A.; Körstgens, V.; Perlich, J.; Roth, S. V.; Müller-Buschbaum, P.

    2012-04-01

    Sol-gel templating combined with iterative spin-coating steps are used to custom-tailor hierarchically structured titania thin films. Using poly(styrene-block-ethylene oxide) P(S-b-PEO) as the structure directing agent, a foam-like structure is combined with nanogranules. Both structural elements are merged into a complex assembly in thin film geometry. The resulting morphology is pictured by SEM and probed with GISAXS. The installed mesoporous titania sandwich structure exhibits holes with a size of 45 nm which makes it promising for applications in photovoltaics or photocatalysis. An optical characterization completes the structural investigation.

  10. Log-rolling block copolymers cylinders

    NASA Astrophysics Data System (ADS)

    Kim, So Youn; Kim, Ye Chan; Kim, Dong Hyup; Kwon, Na Kyung; Register, Richard A.

    Shear has been the most effective method to create long range order of micro- or nano- structures in soft materials. When shear is applied, soft particles or polymers tend to align along the shear direction to minimize the viscous dissipation, thus transverse (so-called ``log-rolling'') alignment is unfavored. In this study, for the first time we report the transverse alignment of cylinder-forming block copolymers. Poly(styrene-b-methyl methacrylate), PS-PMMA, can form a metastable hemicylinder structure when confined in a thin film, and this hemicylinder structure can align either along the shear direction, or transverse to the shear direction (``log-rolling''), depending on the shearing temperature. This unusual ``log-rolling'' behavior is explained by the different chain mobility of the two blocks in PS-PMMA; the rigidity of core cylinder is the critical parameter determining the direction of shear alignment.

  11. Comparing Fluid and Elastic Block Copolymer Shells

    NASA Astrophysics Data System (ADS)

    Rozairo, Damith; Croll, Andrew B.

    2014-03-01

    Emulsions can be stabilized with the addition of an amphiphilic diblock copolymer, resulting in droplets surrounded and protected by a polymer monolayer. Such droplets show considerable promise as advanced cargo carriers in pharmaceuticals or cosmetics due to their strength and responsiveness. Diblock copolymer interfaces remain mostly fluid and may not be able to attain the mechanical performance desired by industry. To strengthen block copolymer emulsion droplets we have developed a novel method for creating thin elastic shells using polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS). Characterization of the fluid filled elastic shells is difficult with traditional means which lead us to develop a new and general method of mechanical measurement. Specifically, we use laser scanning confocal microscopy to achieve a high resolution measure of the deformation of soft spheres under the influence of gravity. To prove the resilience of the technique we examine both a polystyrene-b-poly(ethylene oxide) (PS-PEO) stabilized emulsion and the PS-PAA-PS emulsion. The mechanical measurement allows the physics of the polymer at the interface to be examined, which will ultimately lead to the rational development of these technologies.

  12. Synthesis and morphology characterization of polydimethylsiloxane-containing block copolymers

    NASA Astrophysics Data System (ADS)

    Wadley, Maurice

    The thin film morphology characteristics of polydimethylsiloxane-containing block copolymers have been investigated. For this investigation, a commercially available hydroxyl terminated PDMS was purchased from Gelest and attached to a carboxylic acid functional reversible addition-fragmentation chain transfer (RAFT) agent by Steglich esterification. This produced macro-RAFT agents to which styrene monomer was polymerized. By using this approach the generation of low polydispersity polystyrene-block-polydimethylsiloxane (PS-block-PDMS) copolymers of various molecular weights spanning a wide volume fraction range in which the PDMS block remained the same in each polymerization. Synthesized block copolymers were characterized by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. Bulk and thin film characterization of PS-block-PDMS copolymers was done by small-angle x-ray scattering (SAXS), transmission electron microscopy (TEM), contact angle measurements, scanning force microscopy (SFM), and grazing incidence small-angle X-ray scattering (GISAXS). The following observations have been made. For PS-rich PS-block -PDMS copolymer thin films the low surface tension of PDMS caused it to migrate to the film surface regardless of solvent choice. The surface morphology was found to depend strongly on the solubility parameter of the solvent and exhibited SFM images consistent with parallel cylinder, perforated lamellar, and lamellar surface layers with increasing solvent solubility parameter. This behavior was due to the selective swelling of the individual blocks under slightly selective, good solvent conditions. A custom solvent annealing apparatus provided similar results in which order-order transitions in the thin films were observed with increasing solvent solubility parameter. Additionally improvements in the long-range order were observed after 1 h of solvent annealing. PS-rich PS-block-PDMS copolymer thin films also displayed PDMS

  13. Block copolymer adsorbed layers on solids

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Gowd, Bhoje; Endoh, Maya; Koga, Tadanori

    Block copolymer thin films offer a simple and effective route to fabricate highly ordered periodic microdomain structures. The fundamental, yet unsolved question is whether these highly oriented microdomain structures persist even near an impenetrable solid wall. We here report the adsorbed structures of polystyrene-block-poly (4-vinylpyridine) (PS-block-P4VP, Mw = 41,000, PS (weight fraction =0.81) formed on planar silicon substrates. Perpendicularly aligned cylindrical microdomains were created by solvent vapor annealing (Gowd et al., Soft Matter, 2014, 10, 7753), and the adsorbed layer was derived by solvent leaching with chloroform, a good solvent for the polymers and thereafter characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle x-ray scattering, and x-ray reflectivity. The results showed that both PS and P4VP chains lie flat on the substrate, forming a microphase-separated structure (MSS) without long-range order. Moreover, a spin-coated PS-block-P4VP thin film annealed under vacuum at 190 °C showed similar MSS on the substrate, indicating the generality of the interfacial polymer structure. Details will be discussed in the presentation. NSF Grant No. CMMI-1332499.

  14. Block Copolymer Membranes for Biofuel Purification

    NASA Astrophysics Data System (ADS)

    Evren Ozcam, Ali; Balsara, Nitash

    2012-02-01

    Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

  15. Block copolymer structures in nano-pores

    NASA Astrophysics Data System (ADS)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei

    2010-03-01

    We present results of coarse-grained computer modelling of block copolymer systems in cylindrical and spherical nanopores on Cell Dynamics Simulation. We study both cylindrical and spherical pores and systematically investigate structures formed by lamellar, cylinders and spherical block copolymer systems for various pore radii and affinity of block copolymer blocks to the pore walls. The obtained structures include: standing lamellae and cylinders, ``onions,'' cylinder ``knitting balls,'' ``golf-ball,'' layered spherical, ``virus''-like and mixed morphologies with T-junctions and U-type defects [1]. Kinetics of the structure formation and the differences with planar films are discussed. Our simulations suggest that novel porous nano-containers can be formed by confining block copolymers in pores of different geometries [1,2]. [4pt] [1] M. Pinna, X. Guo, A.V. Zvelindovsky, Polymer 49, 2797 (2008).[0pt] [2] M. Pinna, X. Guo, A.V. Zvelindovsky, J. Chem. Phys. 131, 214902 (2009).

  16. Phase Behavior of Symmetric Sulfonated Block Copolymers

    SciTech Connect

    Park, Moon Jeong; Balsara, Nitash P.

    2008-08-21

    Phase behavior of poly(styrenesulfonate-methylbutylene) (PSS-PMB) block copolymers was studied by varying molecular weight, sulfonation level, and temperature. Molecular weights of the copolymers range from 2.9 to 117 kg/mol. Ordered lamellar, gyroid, hexagonally perforated lamellae, and hexagonally packed cylinder phases were observed in spite of the fact that the copolymers are nearly symmetric with PSS volume fractions between 0.45 and 0.50. The wide variety of morphologies seen in our copolymers is inconsistent with current theories on block copolymer phase behavior such as self-consistent field theory. Low molecular weight PSS-PMB copolymers (<6.2 kg/mol) show order-order and order-disorder phase transitions as a function of temperature. In contrast, the phase behavior of high molecular weight PSS-PMB copolymers (>7.7 kg/mol) is independent of temperature. Due to the large value of Flory-Huggins interaction parameter, x, between the sulfonated and non-sulfonated blocks, PSS-PMB copolymers with PSS and PMB molecular weights of 1.8 and 1.4 kg/mol, respectively, show the presence of an ordered gyroid phase with a 2.5 nm diameter PSS network. A variety of methods are used to estimate x between PSS and PMB chains as a function of sulfonation level. Some aspects of the observed phase behavior of PSS-PMB copolymers can be rationalized using x.

  17. Thermal annealing as an easy tool for the controlled arrangement of gold nanoparticles in block-copolymer thin films

    NASA Astrophysics Data System (ADS)

    Ledo-Suárez, Ana; Hoppe, Cristina Elena; Lazzari, Massimo; Lopez Quintela, M. Arturo; Zucchi, Ileana Alicia

    2013-06-01

    Thermal annealing was used for the bottom-up fabrication of morphologically controlled gold-block-copolymer (Au-BC) nanocomposites. Three different blends formed by polystyrene (PS) homopolymer and PS-coated gold nanoparticles (PSSH@Au) were used as modifiers of asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA): PS26/PS26SH@Au, PS75/PS75SH@Au and PS167/PS167SH@Au (where the subscripts refer to the number of styrene monomeric units). The results indicated that all three blends used as modifiers (PSn/PSnSH@Au) were successfully located in the PS phase during thermally induced BC self-assembly for a composition range from 5 to 43 wt% without macro-phase separation. The PSnSH@Au moiety experienced molecular desorption, nanocrystal core coalescence and partial molecular re-encapsulation processes during thermal annealing, leading to sphere-like gold NPs with a larger average size (without exceeding an interdomain distance). Ligand chain length regulated the degree of coalescence and re-encapsulation, defining ultimate core size. Furthermore, proper combination of chain length and composition enabled tuning of NP partitioning and arrangement on different length scales through thermally activated cooperative assembly processes. These results have not only significant impact for establishing thermal processing as a useful tool for the precise control of NP size and distribution, but also much broader implications for many nanoparticle-based technologies.

  18. Effect of chain topology of block copolymer on micellization: ring vs linear block copolymer

    NASA Astrophysics Data System (ADS)

    Kim, Kwang Hee; Huh, June; Jo, Won Ho

    2003-03-01

    The aggregation of amphiphilic block copolymers in solution to form micelles has attracted great interest in recent years because of its importance in industrial applications. Many studies on these systems have mainly focused on a di- or triblock copolymer and much less attention was given to other architectures such as ring block copolymer. Recent experimental work has extended those works to include ring block copolymer, made by end-linking the triblock copolymer. Although the micellization of the ring block copolymer seemed to be favored over that of the linear triblock copolymer, two block copolymers showed similar values of cmc in experiments. In the present work, micellization of ring block copolymer (ring-B9A8) was simulated by Brownian dyanmics and micellar behavior is compared with triblock copolymer (A4B9A4) to investigate more systematically the effect of molecular architecture. Critical micelle concentration (cmc), average aggregation number and micellar distribution are compared with corresponding quantities measured for linear triblock copolymers having the same chain length and composition. Simulation results show that the cmc of ring-B9A8 is smaller than that of A4B9A4. The difference is explained by simple mean-field type theory.

  19. Electrostatic control of block copolymer morphology

    NASA Astrophysics Data System (ADS)

    Sing, Charles E.; Zwanikken, Jos W.; Olvera de La Cruz, Monica

    2014-07-01

    Energy storage is at present one of the foremost issues society faces. However, material challenges now serve as bottlenecks in technological progress. Lithium-ion batteries are the current gold standard to meet energy storage needs; however, they are limited owing to the inherent instability of liquid electrolytes. Block copolymers can self-assemble into nanostructures that simultaneously facilitate ion transport and provide mechanical stability. The ions themselves have a profound, yet previously unpredictable, effect on how these nanostructures assemble and thus the efficiency of ion transport. Here we demonstrate that varying the charge of a block copolymer is a powerful mechanism to predictably tune nanostructures. In particular, we demonstrate that highly asymmetric charge cohesion effects can induce the formation of nanostructures that are inaccessible to conventional uncharged block copolymers, including percolated phases desired for ion transport. This vastly expands the design space for block copolymer materials and is informative for the versatile design of battery electrolyte materials.

  20. Block copolymers for enhanced oil recovery

    SciTech Connect

    Wu, M.M.; Ball, L.E.

    1987-05-19

    A water soluble block copolymer is described comprising two or more water soluble polymer blocks, wherein the water soluble polymer blocks comprise polymerized monomers. The monomers are selected from the group consisting of acrylamide, methacrylamide, vinyl methyl ether, acrylic and methacrylic acid and their water soluble salts and N-substituted acrylamides.

  1. Arbitrary lattice symmetries via block copolymer nanomeshes

    PubMed Central

    Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.; Yager, Kevin G.

    2015-01-01

    Self-assembly of block copolymers is a powerful motif for spontaneously forming well-defined nanostructures over macroscopic areas. Yet, the inherent energy minimization criteria of self-assembly give rise to a limited library of structures; diblock copolymers naturally form spheres on a cubic lattice, hexagonally packed cylinders and alternating lamellae. Here, we demonstrate multicomponent nanomeshes with any desired lattice symmetry. We exploit photothermal annealing to rapidly order and align block copolymer phases over macroscopic areas, combined with conversion of the self-assembled organic phase into inorganic replicas. Repeated photothermal processing independently aligns successive layers, providing full control of the size, symmetry and composition of the nanoscale unit cell. We construct a variety of symmetries, most of which are not natively formed by block copolymers, including squares, rhombuses, rectangles and triangles. In fact, we demonstrate all possible two-dimensional Bravais lattices. Finally, we elucidate the influence of nanostructure on the electrical and optical properties of nanomeshes. PMID:26100566

  2. Rapid self-assembly of block copolymers to photonic crystals

    DOEpatents

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  3. Field-Based Simulations of Confined Block Copolymers

    NASA Astrophysics Data System (ADS)

    Fredrickson, Glenn

    2009-03-01

    This presentation will discuss field-theoretic simulation methods that can be used to analyze the self-assembly behavior of thin block copolymer films, including films that are laterally confined on a flat substrate and curved films on a spherical manifold. Our studies of lateral confinement have revealed strategies for epitaxially templating microdomain patterns with long-range in-plane order and minimal defects (``graphoepitaxy"), and methods for diversifying the set of stable 2D lattice structures. On the sphere, we have found defective ground state block copolymer morphologies that are analogous to spherical crystalline packings in other contexts, e.g. the Thompson problem and viruses. The methods and findings have applications in block copolymer lithography and in dispersion technology of polymer-stabilized nanoparticles and colloids.

  4. Block copolymer libraries: modular versatility of the macromolecular Lego system.

    PubMed

    Lohmeijer, Bas G G; Wouters, Daan; Yin, Zhihui; Schubert, Ulrich S

    2004-12-21

    The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships. PMID:15599456

  5. Mixing thermodynamics of block-random copolymers

    NASA Astrophysics Data System (ADS)

    Beckingham, Bryan Scott

    Random copolymerization of A and B monomers represents a versatile method to tune interaction strengths between polymers, as ArB random copolymers will exhibit a smaller effective Flory interaction parameter chi; (or interaction energy density X) upon mixing with A or B homopolymers than upon mixing A and B homopolymers with each other, and the ArB composition can be tuned continuously. Thus, the incorporation of a random copolymer block into the classical block copolymer architecture to yield "block-random" copolymers introduces an additional tuning mechanism for the control of structure-property relationships, as the interblock interactions and physical properties can be tuned continuously through the random block's composition. However, typical living or controlled polymerizations produce compositional gradients along the "random" block, which can in turn influence the phase behavior. This dissertation demonstrates a method by which narrow-distribution copolymers of styrene and isoprene of any desired composition, with no measurable down-chain gradient, are synthesized. This synthetic method is then utilized to incorporate random copolymers of styrene and isoprene as blocks into block-random copolymers in order to examine the resulting interblock mixing thermodynamics. A series of well-defined near-symmetric block and block-random copolymers (S-I, Bd-S, I-SrI, S-SrI and Bd-S rI diblocks, where S is polystyrene, I is polyisoprene and Bd is polybutadiene), with varying molecular weight and random-block composition are synthesized and the mixing thermodynamics---via comparison of their interaction energy densities, X---of their hydrogenated derivatives is examined through measurement of the order-disorder transition (ODT) temperature. Hydrogenated derivatives of I-SrI and S-SrI block-random copolymers, both wherein the styrene aromaticity is retained and derivatives wherein the styrene units are saturated to vinylcyclohexane (VCH), are found to hew closely to the

  6. Substrate tolerant direct block copolymer nanolithography.

    PubMed

    Li, Tao; Wang, Zhongli; Schulte, Lars; Ndoni, Sokol

    2016-01-01

    Block copolymer (BC) self-assembly constitutes a powerful platform for nanolithography. However, there is a need for a general approach to BC lithography that critically considers all the steps from substrate preparation to the final pattern transfer. We present a procedure that significantly simplifies the main stream BC lithography process, showing a broad substrate tolerance and allowing for efficient pattern transfer over wafer scale. PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are directly applied on substrates including polymers, silicon and graphene. A single oxygen plasma treatment enables formation of the oxidized PDMS hard mask, PS block removal and polymer or graphene substrate patterning. PMID:26606904

  7. Finding Optimal Templates for the Directed Self-Assembly of Thin Film Block Copolymers with Inverse Self-Consistent Field Theory Simulations

    NASA Astrophysics Data System (ADS)

    Hannon, Adam; Ding, Yi; Bai, Wubin; Ross, Caroline; Alexander-Katz, Alfredo

    2014-03-01

    Achieving sub-10 nm patterns with non-periodic features is a key goal in the development of next generation integrated circuits devices. One route to create such features at this length scale is the directed self-assembly of thin film block copolymers (BCPs). Inverse design methods are becoming a key part in developing templates needed for given target patterns where the required template is both non-intuitive and requires optimization. Here we use a self-consistent field theory based inverse design algorithm to find template solutions for target structures. Recent studies have revealed a wide parameter space with multiple solutions for given target structures. Using fidelity and topology functions, we characterize how well different template solutions yield given target structures and refine these solutions beyond simply being free energy minimum solutions. Experiments using polystyrene- b-polydimethylsiloxane BCPs templated by hydrogen silsesquioxane posts are used for verifying and refining the simulation results. Results show that key factors influencing the fidelity and topology of the samples include the effective volume fraction of the solvent annealed system, size of the posts, and areal post density. Optimization of these parameters achieves refined template solutions with better reproducibility and lower defectivity both computationally and experimentally.

  8. Thermodynamic Interactions in Organometallic Block Copolymers

    SciTech Connect

    Pople, John A

    2002-08-06

    The thermodynamic interactions in anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) copolymers were examined using birefringence, small angle X-ray and neutron scattering (SAXS and SANS). We show that birefringence detection of the order-disorder transition is possible in colored samples provided the wavelength of the incident beam is in the tail of the absorption spectrum. The location of the order-disorder transition was confirmed by SAXS. The temperature-dependence of the Flory-Huggins parameter, {chi}, of SF copolymers, determined by SAXS, is similar in magnitude to that between polystyrene and polyisoprene chains. We find that {chi} is independent of block copolymer composition (within experimental error). We also demonstrate that the neutron scattering length densities of styrene and ferrocenyldimethylsilane moieties are identical due to a surprising cancellation of factors related to density and atomic composition.

  9. Beyond Orientation: The Impact of Electric Fields on Block Copolymers

    SciTech Connect

    Liedel, Clemens; Boker, A.; Pester, Christian; Ruppel, Markus A; Urban, Volker S

    2012-01-01

    Since the first report on electric field-induced alignment of block copolymers (BCPs) in 1991, electric fields have been shown not only to direct the orientation of BCP nanostructures in bulk, solution, and thin films, but also to reversibly induce order-order transitions, affect the order-disorder transition temperature, and control morphologies' dimensions with nanometer precision. Theoretical and experimental results of the past years in this very interesting field of research are summarized and future perspectives are outlined.

  10. Reordering transitions during annealing of block copolymer cylinder phases

    DOE PAGESBeta

    Majewski, Pawel W.; Yager, Kevin G.

    2015-10-06

    While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontalmore » state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.« less

  11. Molecular transfer printing using block copolymers.

    PubMed

    Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang; Nealey, Paul F

    2010-02-23

    Soft lithographic techniques augment or enhance the capabilities of traditional patterning processes and expand the diversity of materials that can be patterned. Realization of robust parallel techniques for creating chemical patterns at the nanoscale has been challenging. Here we present a method for creating and replicating chemical patterns that uses functionalized homopolymer inks that are preferentially segregated into the nanodomains of phase-separated diblock copolymer films. The inks are transferred by reaction to substrates that are brought into contact with block copolymer films, creating chemical patterns on the substrate that mirror the domain structure present at the film surface with high fidelity and resolution. In addition to printing from self-assembled domain structures, we can also direct the assembly of the block copolymer films from which transfer occurs using lithographically defined masters so as to replicate and transfer patterns of inks with controlled and well-defined geometries. The transferred patterns may be at higher resolution than the lithographically defined master, and the process can be repeated to create multiple copies of identical replicas. Transfer of one ink from one block of the copolymer is also possible, and filling the interspatial regions of the pattern with a second ink provides a pathway toward creating patterns with diverse chemical functionalities. PMID:20041629

  12. Influence of substrate interaction and confinement on electric-field-induced transition in symmetric block-copolymer thin films.

    PubMed

    Mukherjee, Arnab; Mukherjee, Rajdip; Ankit, Kumar; Bhattacharya, Avisor; Nestler, Britta

    2016-03-01

    In the present work, we study morphologies arising due to competing substrate interaction, electric field, and confinement effects on a symmetric diblock copolymer. We employ a coarse-grained nonlocal Cahn-Hilliard phenomenological model taking into account the appropriate contributions of substrate interaction and electrostatic field. The proposed model couples the Ohta-Kawasaki functional with Maxwell equation of electrostatics, thus alleviating the need for any approximate solution used in previous studies. We calculate the phase diagram in electric-field-substrate strength space for different film thicknesses. In addition to identifying the presence of parallel, perpendicular, and mixed lamellae phases similar to analytical calculations, we also find a region in the phase diagram where hybrid morphologies (combination of two phases) coexist. These hybrid morphologies arise either solely due to substrate affinity and confinement or are induced due to the applied electric field. The dependence of the critical fields for transition between the various phases on substrate strength, film thickness, and dielectric contrast is discussed. Some preliminary 3D results are also presented to corroborate the presence of hybrid morphologies. PMID:27078402

  13. Influence of substrate interaction and confinement on electric-field-induced transition in symmetric block-copolymer thin films

    NASA Astrophysics Data System (ADS)

    Mukherjee, Arnab; Mukherjee, Rajdip; Ankit, Kumar; Bhattacharya, Avisor; Nestler, Britta

    2016-03-01

    In the present work, we study morphologies arising due to competing substrate interaction, electric field, and confinement effects on a symmetric diblock copolymer. We employ a coarse-grained nonlocal Cahn-Hilliard phenomenological model taking into account the appropriate contributions of substrate interaction and electrostatic field. The proposed model couples the Ohta-Kawasaki functional with Maxwell equation of electrostatics, thus alleviating the need for any approximate solution used in previous studies. We calculate the phase diagram in electric-field-substrate strength space for different film thicknesses. In addition to identifying the presence of parallel, perpendicular, and mixed lamellae phases similar to analytical calculations, we also find a region in the phase diagram where hybrid morphologies (combination of two phases) coexist. These hybrid morphologies arise either solely due to substrate affinity and confinement or are induced due to the applied electric field. The dependence of the critical fields for transition between the various phases on substrate strength, film thickness, and dielectric contrast is discussed. Some preliminary 3D results are also presented to corroborate the presence of hybrid morphologies.

  14. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  15. Regulating block copolymer phases via selective homopolymers.

    PubMed

    Yang, Shuang; Lei, Zhen; Hu, Nan; Chen, Er-Qiang; Shi, An-Chang

    2015-03-28

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer. PMID:25833605

  16. Regulating block copolymer phases via selective homopolymers

    SciTech Connect

    Yang, Shuang E-mail: eqchen@pku.edu.cn; Lei, Zhen; Hu, Nan; Chen, Er-Qiang E-mail: eqchen@pku.edu.cn; Shi, An-Chang

    2015-03-28

    The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer.

  17. Diamond-Forming Block Copolymers and Diamond-like Morphologies: a New Route towards efficient Block Copolymer Membranes?

    NASA Astrophysics Data System (ADS)

    Erukhimovich, Igor; Kriksin, Yury

    2014-03-01

    Formation of ordered (microphase separated) block copolymer nanostructures is a promising route towards creating isoporous membranes suitable for technological applications. We propose a new route to achieve this target: to choose such block copolymer architectures, which would provide a practically isotropic permeability both in the bulk and in thin films. Basing both on the weak segregation theory extension into the thin films and the self-consistent field theory numerical procedure we present the results concerning the effects of the wall confinement both with neutral, selective and patterned walls on the structure and stability of the block copolymer ordered films. The diamond-like morphology is found to be the most promising one as to optimizing the permeability of thin films. A new effect of the diamond morphology stability enhancement in the presence of a properly designed lamellar-like wall pattern is discovered and the corresponding phase diagram demonstrating the effect of the pattern scale and film width on the diamond morphology stability is presented. The financial support was provided by Ministry of Science and Education of Russian Federation (State Contract No. 02.740.11.0858) and European Commission (FP7 project NMP3-SL-2009- 228652 (SELFMEM)).

  18. Block copolymer blend phase behavior: Binary diblock blends and amphiphilic block copolymer/epoxy mixtures

    NASA Astrophysics Data System (ADS)

    Lipic, Paul Martin

    The phase behavior of block copolymers and block copolymer blends has provided an extensive amount of exciting research and industrial applications for over thirty years. However, the unique nanoscale morphologies of microphase separated block copolymer systems is still not completely understood. This thesis examines the phase behavior of diblock copolymers and binary diblock copolymer blends in the strong segregation limit (SSL), and blends of an amphiphilic diblock copolymer with an epoxy resin. Studies of high molecular weight (˜84,000 g/mole) poly(ethylene)-poly(ethyl ethylene) (PE-PEE) diblock copolymers probed the ability of block copolymers to reach equilibrium in the SSL. Samples of pure diblocks or binary diblock blends prepared using different preparation techniques (solvent casting or precipitation) had different phase behaviors, as identified with transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS), confirming non-equilibrium phase behavior. This non-equilibrium behavior was metastable, and these results identify the caution that should be used when claiming equilibrium phase behavior in the SSL. Blends of an amphiphilic diblock copolymer, poly(ethylene oxide)-poly(ethylene-alt-propylene) (PEO-PEP) with a polymerizable epoxy resin selectively miscible with PEO, poly(Bisphenol-A-co-epichlorohydrin), supported theoretical calculations and increased the understanding of block copolymer/homopolymer blends. These blends formed different ordered structures (lamellae, bicontinuous cubic gyroid, hexagonally packed cylinders, cubic and hexagonally packed spheres) as well as a disordered spherical micellar structure, identified with SAXS and rheological measurements. Addition of hardener, methylene dianiline, to the system resulted in cross-linking of the epoxy resin and formation of a thermoset material. Macrophase separation between the epoxy and block copolymer did not occur, but local expulsion of the PEO from the epoxy was

  19. Rod-Coil Block Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

    2005-01-01

    This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

  20. Dynamics of Block Copolymer Nanocomposites

    SciTech Connect

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  1. Hierarchical porous polymer scaffolds from block copolymers.

    PubMed

    Sai, Hiroaki; Tan, Kwan Wee; Hur, Kahyun; Asenath-Smith, Emily; Hovden, Robert; Jiang, Yi; Riccio, Mark; Muller, David A; Elser, Veit; Estroff, Lara A; Gruner, Sol M; Wiesner, Ulrich

    2013-08-01

    Hierarchical porous polymer materials are of increasing importance because of their potential application in catalysis, separation technology, or bioengineering. Examples for their synthesis exist, but there is a need for a facile yet versatile conceptual approach to such hierarchical scaffolds and quantitative characterization of their nonperiodic pore systems. Here, we introduce a synthesis method combining well-established concepts of macroscale spinodal decomposition and nanoscale block copolymer self-assembly with porosity formation on both length scales via rinsing with protic solvents. We used scanning electron microscopy, small-angle x-ray scattering, transmission electron tomography, and nanoscale x-ray computed tomography for quantitative pore-structure characterization. The method was demonstrated for AB- and ABC-type block copolymers, and resulting materials were used as scaffolds for calcite crystal growth. PMID:23908232

  2. Monte Carlo simulations of the phase separation of a copolymer blend in a thin film.

    PubMed

    Wang, Zhexiao; Shao, Jing; Pan, Heng; Feng, Xiaoshuang; Chen, Peng; Xia, Ru; Wu, Xiangsong; Qian, Jiasheng

    2015-02-23

    Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures. PMID:25504337

  3. Synthesis and Application of Conducting Block Copolymers in Organic Photovoltaics

    NASA Astrophysics Data System (ADS)

    Boudouris, Bryan W.; Hillmyer, Marc A.; Frisbie, C. Daniel

    2007-03-01

    Recent advances in the fabrication and post-processing of polymer -- fullerene bulk heterojunction solar cells have allowed for devices with power conversion efficiencies up to 5% to be generated. An understanding of how the internal morphology of the active layer affects device performance would facilitate optimization and ultimately lead to higher efficiencies. Block copolymers have been shown to self-assemble into well-structured, microphase-separated domains on the order of the diffusion length (˜ 10 nm) of an exciton (bound electron-hole pair) in thin films. In an effort to make a nanostructured active layer morphology we have synthesized block copolymers where the conducting moiety is either poly(3-hexylthiophene) or poly(3-dodeclythiophene) and the second, etchable block is polylactide. Hydroxyl-terminated polythiophene molecules were synthesized via the McCullough method and used as macroinitiators for the ring-opening polymerization of D,L-lactide. AFM images of spin-coated block copolymer films show separation between the polythiophene and polylactide segments. After subjecting the samples to a dilute aqueous base for short periods of time, we have selectively etched the polylactide segments to create pits in the semicrystalline polythiophene matrices. In addition to these findings, preliminary device results will also be discussed.

  4. Combinatorial Block Copolymer Ordering on Tunable Rough

    SciTech Connect

    Kulkarni M. M.; Yager K.; Sharma, A.; Karim, A.

    2012-05-01

    Morphology control of block copolymer (BCP) thin films through substrate interaction via controlled roughness parameters is of significant interest for numerous high-tech applications ranging from solar cells to high-density storage media. While effects of substrate surface energy (SE) and roughness (R) on BCP morphology have been individually investigated, their synergistic effects have not been explored in any systematic manner. Interestingly, orientation response of BCP to changes in SE can be similar to what can be accomplished with variations in R. Here we present a novel approach for orienting lamellar BCP films of poly(styrene)-block-poly(methyl methacrylate) (PS-PMMA) on spin-coated xerogel (a dried gel of silica nanoparticle network) substrate with simultaneously tunable surface energy, {gamma}{sub s} {approx} 29-53 mJ/m{sup 2}, by UVO exposure and roughness, R{sub rms} {approx} 0.5-30 nm, by sol-gel processing steps of regulating the catalyst concentration and sol aging time. As in previous BCP orientation studies on 20 nm diameter monodisperse silica nanoparticle coated surface, we find a similar but broadened oscillatory BCP orientation behavior with film thickness due to the random rather than periodic rough surfaces. We also find that higher random roughness amplitude is not the necessary criteria for obtaining a vertical orientation of BCP lamellae. Rather, a high surface fractal dimension (D{sub f} > 2.4) of the rough substrate in conjunction with an optimal substrate surface energy {gamma}{sub s} 29 mJ/m{sup 2} results in 100% vertically oriented lamellar microdomains. The AFM measured film surface microstructure correlates well with the internal 3D BCP film structure probed by grazing incidence small-angle X-ray scattering (GISAXS) and rotational small-angle neutron scattering (SANS). In contrast to tunable self-assembled monolayer (SAM)-coated substrates, the xerogel films are very durable and retain their chemical properties over period of

  5. Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation.

    PubMed

    Fan, Yin; Tang, Shengchang; Thomas, Edwin L; Olsen, Bradley D

    2014-11-25

    Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins. PMID:25393374

  6. Perspective: Evolutionary design of granular media and block copolymer patterns

    NASA Astrophysics Data System (ADS)

    Jaeger, Heinrich M.; de Pablo, Juan J.

    2016-05-01

    The creation of new materials "by design" is a process that starts from desired materials properties and proceeds to identify requirements for the constituent components. Such process is challenging because it inverts the typical modeling approach, which starts from given micro-level components to predict macro-level properties. We describe how to tackle this inverse problem using concepts from evolutionary computation. These concepts have widespread applicability and open up new opportunities for design as well as discovery. Here we apply them to design tasks involving two very different classes of soft materials, shape-optimized granular media and nanopatterned block copolymer thin films.

  7. Are block copolymer worms more effective Pickering emulsifiers than block copolymer spheres?

    PubMed

    Thompson, K L; Mable, C J; Cockram, A; Warren, N J; Cunningham, V J; Jones, E R; Verber, R; Armes, S P

    2014-11-21

    RAFT-mediated polymerisation-induced self-assembly (PISA) is used to prepare six types of amphiphilic block copolymer nanoparticles which were subsequently evaluated as putative Pickering emulsifiers for the stabilisation of n-dodecane-in-water emulsions. It was found that linear poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) diblock copolymer spheres and worms do not survive the high shear homogenisation conditions used for emulsification. Stable emulsions are obtained, but the copolymer acts as a polymeric surfactant; individual chains rather than particles are adsorbed at the oil-water interface. Particle dissociation during emulsification is attributed to the weakly hydrophobic character of the PHPMA block. Covalent stabilisation of these copolymer spheres or worms can be readily achieved by addition of ethylene glycol dimethacrylate (EGDMA) during the PISA synthesis. TEM studies confirm that the resulting cross-linked spherical or worm-like nanoparticles survive emulsification and produce genuine Pickering emulsions. Alternatively, stabilisation can be achieved by either replacing or supplementing the PHPMA block with the more hydrophobic poly(benzyl methacrylate) (PBzMA). The resulting linear spheres or worms also survive emulsification and produce stable n-dodecane-in-water Pickering emulsions. The intrinsic advantages of anisotropic worms over isotropic spheres for the preparation of Pickering emulsions are highlighted. The former particles are more strongly adsorbed at similar efficiencies compared to spheres and also enable smaller oil droplets to be produced for a given copolymer concentration. The scalable nature of PISA formulations augurs well for potential applications of anisotropic block copolymer nanoparticles as Pickering emulsifiers. PMID:25254485

  8. Oriented Protein Nanoarrays on Block Copolymer Template.

    PubMed

    Shen, Lei; Zhu, Jintao

    2016-03-01

    Here, a simple yet robust method is developed to fabricate oriented protein nanoarrays by employing a block copolymer (BCP) template, which presents nano-scaled spot areas at high-density arrays. Unlike the conventional BCP nanolithography, the BCP platform described here resists nonspecific protein adsorption and prevents the denaturation of immobilized proteins in aqueous solution. The orderly arranged array areas are functionalized by linking chemistry which allows for the precise control of protein orientation. This approach allows us to generate potentially oriented protein nanoarrays at high-density array spots, which is useful for miniaturized nanoarrays within high-throughput proteomic applications. PMID:26785818

  9. Tunable Morphologies from Charged Block Copolymers

    SciTech Connect

    Goswami, Monojoy; Sumpter, Bobby G; Mays, Jimmy; Messman, Jamie M

    2010-01-01

    The bulk morphologies formed by a new class of charged block copolymers, 75 vol % fluorinated polyisoprene (FPI) 25 vol% sulfonated polystyrene (PSS) with 50% sulfonation, are characterized, and the fundamental underlying forces that promote the self-assembly processes are elucidated. The results show how the bulk morphologies are substantially different from their uncharged diblock counterparts (PS-PI) and also how morphology can be tuned with volume fraction of the charged block and the casting solvent. A physical understanding based on the underlying strong electrostatic interactions between the charged block and counterions is obtained using Monte Carlo (MC) and Molecular Dynamics (MD) simulations. The 75/25 FPI-PSS shows hexagonal morphologies with the minority blocks (PSS) forming the continuous phase due to charge percolation and the FPI blocks arranged in hexagonal cylinders. Some long-range order can be sustained even if lipophobicity is increased (addition of water), albeit with lower dimensional structures. However, thermal annealing provides sufficient energy to disrupt the percolated charges and promotes aggregation of ionic sites which leads to a disordered system. Diverse and atypical morphologies are readily accessible by simply changing the number distribution of the charges on PSS block.

  10. Fabrication of Complex Three-Dimensional Nanostructures from Self-Assembling Block Copolymer Materials on Patterned Surfaces: A computational Study

    NASA Astrophysics Data System (ADS)

    Ye, Xianggui; Edwards, Brian J.; Khomami, Bamin

    2010-03-01

    Chemically patterned substrates can direct the assembly of adsorbed layers or thin films of block copolymers. Here, we consider the self-assembly of a lamella-forming diblock copolymer on periodically stripe-patterned substrates. The morphology of the block copolymer follows the pattern at the substrate; however, with an increasing degree of mismatch between the width of the stripe-pattern and the periodic spacing of bulk block copolymer, novel morphologies have been found. Therefore, it is possible to adjust the morphologies in thin bock copolymer films by adjusting the mismatch between the width of the stripe-pattern and the periodic spacing of the bulk block copolymer. These results demonstrate a promising strategy for fabrication of complex interfacial nanostructures from chemically patterned templates.

  11. Interface-enforced complexation between copolymer blocks.

    PubMed

    Steinschulte, Alexander A; Xu, Weinan; Draber, Fabian; Hebbeker, Pascal; Jung, Andre; Bogdanovski, Dimitri; Schneider, Stefanie; Tsukruk, Vladimir V; Plamper, Felix A

    2015-05-14

    Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering. PMID:25807174

  12. Controlling Structure in Sulfonated Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Truong, Phuc; Stein, Gila; Strzalka, Joe

    2015-03-01

    In many ionic block copolymer systems, the strong incompatibility between ionic and non-ionic segments will trap non-equilibrium structures in the film, making it difficult to engineer the optimal domain sizes and transport pathways. The goal of this work is to establish a framework for controlling the solid-state structure of sulfonated pentablock copolymer membranes. They have ABCBA block sequence, where A is poly(t-butyl styrene), B is poly(hydrogenated isoprene), and C is poly(styrene sulfonate). To process into films, the polymer is dissolved in toluene/n-propanol solvent mixtures, where the solvent proportions and the polymer loading were both varied. Solution-state structure was measured with small angle X-ray scattering (SAXS). We detected micelles with radii that depend on the solvent composition and polymer loading. Film structure was measured with grazing-incidence SAXS, which shows (i) domain periodicity is constant throughout film thickness; (ii) domain periodicity depends on solvent composition and polymer loading, and approximately matches the micelle radii in solutions. The solid-state packing is consistent with a hard sphere structure factor. Results suggest that solid-state structure can be tuned by manipulating the solution-state self-assembly.

  13. Method of producing nanopatterned articles using surface-reconstructed block copolymer films

    SciTech Connect

    Russell, Thomas P; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

    2013-08-27

    Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

  14. Theory of Chirality Transfer in Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Prasad, Ishan; Grason, Gregory

    Block copolymers assemble into a rich spectrum of ordered phases, with complexity driven by asymmetry in copolymer architecture. Despite decades of study, influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has been largely instrumental in prediction of physical properties of polymeric systems. Recently, a polar orientational self-consistent field (oSCF) theory was adopted to model chiral block copolymers having a thermodynamic preference for cholesteric ordering in chiral segments, and which confirmed the equilibrium stability of a helical cylinder morphology observed for chiral diblocks. Here, I describe a newly developed oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar interactions, and focus our study on intra-domain nematic ordering in flexible block copolymer assemblies, and in particular, mechanisms of transfer of segment chirality to mesochiral symmetries of self-assembled bicontinuous network morphologies.

  15. Piezoelectric Properties of Non-Polar Block Copolymers

    SciTech Connect

    Pester, Christian; Ruppel, Markus A; Schoberth, Heiko; Schmidt, K.; Liedel, Clemens; Van Rijn, Patrick; Littrell, Ken; Schindler, Kerstin; Hiltl, Stephanie; Czubak, Thomas; Mays, Jimmy; Urban, Volker S; Boker, Alexander

    2011-01-01

    Piezoelectric properties in non-polar block copolymers are a novelty in the field of electroactive polymers. The piezoelectric susceptibility of poly(styrene-b-isoprene) block copolymer lamellae is found to be up to an order of magnitude higher when compared to classic piezoelectric materials. The electroactive response increases with temperature and is found to be strongest in the disordered phase.

  16. Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

    PubMed

    Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

    2015-04-14

    Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation. PMID:25811763

  17. Block Copolymer Templates for Optical Materials and Devices

    NASA Astrophysics Data System (ADS)

    Urbas, Augustine; Martin, Maldovan; Carter, W. C.; Thomas, E. L.; Fasolka, Michael; Fraser, Cassandra

    2002-03-01

    Block copolymers can act as super-lattices for creating novel optical structures. We have fabricated block copolymer photonic crystals from one, two and three dimensionally periodic systems and have enhanced their dielectric properties towards creating complete 3D band gaps. By using carefully selected blends of linear and star block copolymers, we are able to create hierarchical blends which exhibit precise molecular positioning of fluorescent molecules. We are exploring these unique patterning capabilities of block copolymer systems for the formation of ordered arrays of optically active components within a photonic crystal. Precise location of both fluorescent and nonlinear components within block copolymer photonic crystals affords new opportunities for creating low threshold, upconverting and array lasers as well as optical modulators and other photonic devices.

  18. Light-emitting block copolymers composition, process and use

    DOEpatents

    Ferraris, John P.; Gutierrez, Jose J.

    2006-11-14

    Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

  19. Anomalous Micellization of Pluronic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

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

  20. Block copolymer ion gels for gas separation

    NASA Astrophysics Data System (ADS)

    Gu, Yuanyan; Lodge, Timothy

    2012-02-01

    Carbon dioxide removal from light gases (eg. N2, CH4, and H2) is a very important technology for industrial applications such as natural gas sweetening, CO2 capture from coal-fire power plant exhausts and hydrogen production. Current CO2 separation method uses amine-absorption, which is energy-intensive and requires frequent maintenance. Membrane separation is a cost-effective solution to this problem, especially in small-scale applications. Ionic liquids have recently received increasing interest in this area because of their selective solubility for CO2 and non-volatility. However, ionic liquid itself lacks the persistent structure and mechanical integrity to withstand the high pressure for gas separation. Here, we report the development and gas separation performances of physically crosslinked ion gels based on self-assembly of ABA-triblock copolymers in ionic liquids. Three different types of polymers was used to achieve gelation in ionic liquids. Specifically, a triblock copolymer ion gel with a polymerized ionic liquid mid-block shows performances higher than the upper bound of well-known ``Robeson Plot'' for CO2/N2.

  1. Reflectivity studies on adsorbed block copolymers under shear

    SciTech Connect

    Smith, G.S.; Wages, S.; Baker, S.M.; Toprakcioglu, C.; Hadziioannou, G.

    1994-12-01

    The authors report neutron reflectivity data on (poly)styrene-(poly)ethylene oxide (PS-PEO) diblock copolymers adsorbed onto quartz from the selective solvent cyclohexane (a non-solvent for PEO and a poor solvent for PS). The PEO ``anchor block`` adsorbs strongly to form a thin layer on the quartz substrate, while the deuterated PS chains dangle into the solvent. They find that under static conditions the density profile of the PS block in a poor solvent can be well described by a Schultz function which is indicative of a polymer ``mushroom.`` Furthermore, they have studied the same system under shear at shear rates from 0--400s{sup {minus}1}. They find that there is a dramatic increase in the thickness of the PS layer under shear in cyclohexane and that the relaxation time from the shear-on profile back to the static profile is on the order of several days.

  2. Equilibrium and Kinetics of Block Copolymers Micelles

    NASA Astrophysics Data System (ADS)

    Mysona, Joshua; Morse, David

    Both equilibrium properties of micelles, such as the critical micelle concentration (CMC), and dynamical properties such as the micelle lifetime are difficult to study in simulations because of the slow dynamics of the processes by which micelles are created and destroyed. We first discuss a method of precisely identifying the CMC in a simple model of block copolymer micelles in a homopolymer matrix, which makes use of thermodynamic integration to compute the free energy of formation. We then examine the free energy barriers to competing mechanisms for creating and destroying micelles, which could occur predominantly either by a step-wise process involving insertion and extraction of single molecules or by fission and fusion of entire micelles.

  3. Structure property relations in glassy-semicrystalline block copolymers

    NASA Astrophysics Data System (ADS)

    Khanna, Vikram

    The ability of block copolymers to segregate into nanoscale morphologies makes them a versatile class of engineering materials. This work investigates the relation between the block copolymer structure and its mechanical properties, film dynamics and diffusion kinetics. The first part investigates the influence of structure on the mechanical properties of poly(cyclohexylethylene)-poly(ethylene) (PCHE-PE) block copolymer films. For lamellar block copolymers the mechanical properties depend significantly on the chain architecture (diblock, triblock and pentablock). Diblock copolymer films show complete failure at small strains and pentablock copolymer films show the toughest, response. Moreover, the orientation of the cylinders in a cylinder forming pentablock copolymer affects the toughness of the block copolymer films. In the second part, the effect of surface energy and chain architecture on the orientation of microdomains in the same block copolymer films is investigated. Cylindrical and lamellar triblock copolymers with a PE midblock orient their microdomains normal to the surface. However, a lamellar diblock copolymer prefers a parallel orientation of the sheets with an E surface. Moreover, a cylindrical triblock copolymer with a reduced surface energy poly(ethylene-butylene) midblock orders with the cylinder domains oriented parallel to the surface. Self-consistent field theory calculations suggest that the entropic cost of forming a wetting layer comprised entirely of looping blocks for the triblock architecture, a constraint absent in diblock copolymers, stabilizes the perpendicular orientation. Thus in triblock copolymers, parallel orientations are only stabilized when the surface energy of the midblock is small enough to compensate for this conformational penalty. Finally, a study of the diffusion kinetics of cylinder forming poly(styrene)-poly(ethylene) triblock (SES) and pentablock (SESES) copolymers suggests that for similar molecular weights SESES

  4. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, Michael S.; Saunders, Randall

    1997-01-01

    Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

  5. Morphological studies on block copolymer modified PA 6 blends

    SciTech Connect

    Poindl, M. E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C. E-mail: christian.bonten@ikt.uni-stuttgart.de

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  6. Morphological studies on block copolymer modified PA 6 blends

    NASA Astrophysics Data System (ADS)

    Poindl, M.; Bonten, C.

    2014-05-01

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  7. Molecular Transfer Printing Using Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang; Nealey, Paul

    2009-03-01

    We report a new parallel patterning technique, molecular transfer printing (MTP), for replicating geometrically complex patterns over macroscopic areas with sub-15 nm feature dimensions, and the ability to replicate the same pattern multiple times. In MTP, inks are mixed with block copolymers (BCPs) and deposited as films on a substrate. The inks are compatible with only one block of the BCP, and sequestered into domains of nanometer scale dimensions after microphase separation. A second substrate is then placed in contact with the surface of the film. By designing the inks to react, adsorb, or otherwise interact with the second substrate, inks are transferred to the second substrate in the exact pattern of domains present at the surface of the ``master'' BCP film. Here we demonstrate high degrees of perfection on both line and dot patterns. We also show that 1) the master template can be regenerated, 2) the resultant replica can be used to direct the assembly of BCPs and as a daughter master for MTP, and 3) the master and daughter templates can be reused tens of times.

  8. Nanopatterning of recombinant proteins and viruses using block copolymer templates

    NASA Astrophysics Data System (ADS)

    Cresce, Arthur Von Wald

    The study of interfaces is important in understanding biological interactions, including cellular signaling and virus infection. This thesis is an original effort to examine the interaction between a block copolymer and both a protein and a virus. Block copolymers intrinsically form nanometer-scale structures over large areas without expensive processing, making them ideal for the synthesis of the nanopatterned surfaces used in this study. The geometry of these nanostructures can be easily tuned for different applications by altering the block ratio and composition of the block copolymer. Block copolymers can be used for controlled uptake of metal ions, where one block selectively binds metal ions while the other does not. 5-norbornene-2,3-dicarboxylic acid is synthesized through ring-opening metathesis polymerization. It formed spherical domains with spheres approximately 30 nm in diameter, and these spheres were then subsequently loaded with nickel ion. This norbornene block copolymer was tested for its ability to bind histidine-tagged green fluorescent protein (hisGFP), and it was found that the nickel-loaded copolymer was able to retain hisGFP through chelation between the histidine tag and the metal-containing portions of the copolymer surface. Poly(styrene-b-4-vinylpyridine) (PS/P4VP) was also loaded with nickel, forming a cylindrical microstructure. The binding of Tobacco mosaic virus and Tobacco necrosis virus was tested through Tween 20 detergent washes. Electron microscopy allowed for observation of both block copolymer nanostructures and virus particles. Results showed that Tween washes could not remove bound Tobacco mosaic virus from the surface of PS/P4VP. It was also seen that the size and tunability of block copolymers and the lack of processing needed to attain different structures makes them attractive for many applications, including microfluidic devices, surfaces to influence cellular signaling and growth, and as a nanopatterning surface for

  9. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    PubMed Central

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana P.; Peinemann, Klaus-Viktor

    2015-01-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected. PMID:26471862

  10. Obtaining Perpendicular Block Copolymer Morphologies with Solvent Annealing

    NASA Astrophysics Data System (ADS)

    Gotrik, Kevin; Son, Jeong Gon; Hannon, Adam; Ross, Caroline

    2012-02-01

    Being able to control block copolymer (BCP) thin film morphology and orientation is of interest for lithographic applications where creation of feature sizes ranging from 10-100nm is desirable. Perpendicular oriented cylinders and lamellae are especially valuable due to their high aspect ratios but are difficult to achieve in BCP systems with a large Flory-Huggins interaction parameter (χ). We explore the morphological phase behavior that films (30-200nm) of poly(styrene-b-dimethylsiloxane) (PS-PDMS, 45kg/mol, χ=0.26) exhibit under different solvent conditions with focus on conditions that produce perpendicular microdomains. The microdomains are revealed by selectively etching the PS with an oxygen plasma (50W CF4). Variation in the solvent vapor conditions results in selective swelling of the different blocks of the copolymer depending on the relative Hildebrand solubility parameters (e.g. PS- 18.5, toluene-18.3 MPâ(1/2)), affecting the microdomain morphologies, and the solvent evaporation and deswelling process influences the orientation of the microdomains. Two different strategies are presented involving solvent vapor annealing that result in perpendicular morphologies in films of PS-PDMS and the results are compared with self-consistent field theory modeling of solvent-polymer systems.

  11. Tunable Cosolvent Annealing Affects on Block Copolymer Morphology

    NASA Astrophysics Data System (ADS)

    Gotrik, Kevin; Son, Jeong Gon; Hannon, Adam; Alexander-Katz, Alfredo; Ross, Caroline

    2011-03-01

    Being able to precisely and reproducibly control block copolymer (BCP) morphology is of interest for lithographic applications due to the techniques ability to result in feature sizes ranging from 10-100nm. We explore the morphological phase behavior that thin films (30-40nm) of poly(styrene-b-dimethylsiloxane) (PS-PDMS, 45kg/mol, ~ 0.26 segmental Flory-Huggins interaction parameter) exhibit under different cosolvent vapors of toluene and heptane. Variation in the solvent conditions results in selective swelling of the different blocks of the copolymer depending on relative Hildebrand solubility parameters (e.g. PS- 18.5, toluene-18.3 (MPa)1/2) resulting in cylinders, spheres, lamella, and perforatted lamella self-assembled features which can be revealed by selectively etching the PS with an oxygen plasma (50W CF4). Here we describe precision solvent vapor control while doing in situ spectral reflectometry (230-1500nm) to track swelling of the BCP films as a function of time to gain insight into this BCP system.

  12. Hollow ZIF-8 Nanoworms from Block Copolymer Templates

    NASA Astrophysics Data System (ADS)

    Yu, Haizhou; Qiu, Xiaoyan; Neelakanda, Pradeep; Deng, Lin; Khashab, Niveen M.; Nunes, Suzana P.; Peinemann, Klaus-Viktor

    2015-10-01

    Recently two quite different types of “nano-containers” have been recognized as attractive potential drug carriers; these are wormlike filamenteous micelles (“filomicelles”) on the one hand and metal organic frameworks on the other hand. In this work we combine these two concepts. We report for the first time the manufacturing of metal organic framework nanotubes with a hollow core. These worm-like tubes are about 200 nm thick and several μm long. The preparation is simple: we first produce long and flexible filament-shaped micelles by block copolymer self-assembly. These filomicelles serve as templates to grow a very thin layer of interconnected ZIF-8 crystals on their surface. Finally the block copolymer is removed by solvent extraction and the hollow ZIF-8 nanotubes remain. These ZIF-NTs are surprisingly stable and withstand purification by centrifugation. The synthesis method is straightforward and can easily be applied for other metal organic framework materials. The ZIF-8 NTs exhibit high loading capacity for the model anti cancer drug doxorubicin (DOX) with a pH-triggered release. Hence, a prolonged circulation in the blood stream and a targeted drug release behavior can be expected.

  13. Surface Structure of Thin Films of Multifunctional Ionizable Copolymers

    NASA Astrophysics Data System (ADS)

    Wickramasinghe, Anuradhi; Perahia, Dvora

    Phase segregation results in a rich variety of structures in co-polymers where interfacial forces often dominate the structure of thin films. Introduction of ionizable segments often drives the formation of compounded structures with multiple blocks residing at the interfaces. Here we probe thin films, 40-50nm, of an A-B-C-B-A co-polymer where C is a randomly sulfonated polystyrene with sulfonation fractions of 0, 26 and 52 mole %, B is poly (ethylene-r-propylene), and A is poly (t-butyl styrene) as the sulfonation level and temperature are varied using Neutron Reflectivity AFM, and surface tension measurements. As cast films form layers with both hydrophobic blocks dominating the solid and air interfaces and the ionizable block segregating to the center. Following annealing at 1700C, above Tg of styrene sulfonate, the films coarsen, with surface aggregation dominating the structure, though interfacial regions remain dominated by the hydrophobic segments. We show that in contrast to non-ionic co-polymers, formation of micelles dominated the structure of these ionic structured films. Supported in part by DOE Grant No. DE-SC007908.

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

    NASA Astrophysics Data System (ADS)

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

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

  15. Macroscopic phase decomposition in block copolymers driven by thermooxidative reactions

    NASA Astrophysics Data System (ADS)

    Fan, Shaobin

    Macroscopic phase separations have been observed in a commercial styrene- block-butadiene-block-styrene (SBS) triblock copolymer (Kraton 1102), an as-synthesized SBS triblock copolymer, an as-synthesized styrene-block-butadiene (SB) diblock copolymer and a commercial styrene-block-isoprene-block-styrene (SIS) triblock copolymer (Kraton 1107) at elevated temperatures. To the best of our knowledge, this is the first report on macroscopic phase separations in neat copolymers, including block copolymers. The temporal evolution of the structure, growth dynamics, origin and mechanism of the macroscopic phase separations have been investigated. A theoretical model has been established to describe such phase separation in SB diblock copolymer and numerical simulations have been undertaken to predict the structure evolution and growth dynamics. For styrene-butadiene block copolymers, the phase transition process consists of the first and second phase separations. The origin of such phase separations is attributed to chain scission and crosslinking reactions due to thermooxidative degradation. The formation of phase separated domains is the result of separation of polystyrene-rich domains from polybutadiene-rich domains. A mechanism, termed secondary spinodal decomposition, has been proposed to explain second phase separation. It has also demonstrated that the theoretical model and numerical simulations capture the essential features of the experimental observations. Growth rate was seen to depend on phase separation as well as reaction kinetics. The universal scaling laws have been shown to be invalid in macroscopic phase separations of styrene-butadiene block copolymers. The macroscopic phase separation process is more complex in the SIS triblock copolymer. It consists of a first phase separation, phase dissolution and a second phase separation. The origin of such phase decompositions has been shown to be a progressive chain scission reaction during thermal oxidative

  16. Computer simulations of block copolymer tethered nanoparticle self-assembly

    NASA Astrophysics Data System (ADS)

    Chan, Elaine R.; Ho, Lin C.; Glotzer, Sharon C.

    2006-08-01

    We perform molecular simulations to study the self-assembly of block copolymer tethered cubic nanoparticles. Minimal models of the tethered nanoscale building blocks (NBBs) are utilized to explore the structures arising from self-assembly. We demonstrate that attaching a rigid nanocube to a diblock copolymer affects the typical equilibrium morphologies exhibited by the pure copolymer. Lamellar and cylindrical phases are observed in both systems but not at the corresponding relative copolymer tether block fractions. The effect of nanoparticle geometry on phase behavior is investigated by comparing the self-assembled structures formed by the tethered NBBs with those of their linear ABC triblock copolymer counterparts. The tethered nanocubes exhibit the conventional triblock copolymer lamellar and cylindrical phases when the repulsive interactions between different blocks are symmetric. The rigid and bulky nature of the cube induces interfacial curvature in the tethered NBB phases compared to their linear ABC triblock copolymer counterparts. We compare our results with those structures obtained from ABC diblock copolymer tethered nanospheres to further elucidate the role of cubic nanoparticle geometry on self-assembly.

  17. Graphoepitaxy of self-assembled block copolymers on two-dimensional periodic patterned templates.

    PubMed

    Bita, Ion; Yang, Joel K W; Jung, Yeon Sik; Ross, Caroline A; Thomas, Edwin L; Berggren, Karl K

    2008-08-15

    Self-assembling materials are the building blocks of bottom-up nanofabrication processes, but they need to be templated to impose long-range order and eliminate defects. In this work, the self-assembly of a thin film of a spherical-morphology block copolymer is templated using an array of nanoscale topographical elements that act as surrogates for the minority domains of the block copolymer. The orientation and periodicity of the resulting array of spherical microdomains are governed by the commensurability between the block copolymer period and the template period and is accurately described by a free-energy model. This method, which forms high-spatial-frequency arrays using a lower-spatial-frequency template, will be useful in nanolithography applications such as the formation of high-density microelectronic structures. PMID:18703736

  18. Manipulating Ordering Transitions in Interfacially Modified Block Copolymers

    SciTech Connect

    Singh, N.; Tureau, M; Epps, T

    2009-01-01

    We report a synthetic strategy that allows us to manipulate the interfacial region between blocks and control ordering transitions in poly(isoprene-b-styrene) [P(I-S)] block copolymers. This interfacial modification is accomplished by combining a semi-batch feed with anionic polymerization techniques. Using this approach, we are able to control the segmental composition and molecular interactions in our phase-separated block copolymers, independent of molecular weight and block constituents. A library of copolymers is prepared with various interfacial modifications to examine the effect of interfacial composition on copolymer self-assembly. The morphological characteristics of the self-assembled structures are investigated using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). Normal and inverse tapered block copolymers, containing approximately 15-35 vol% tapered material, show a measurable decrease in the order-disorder transition temperature (TODT) relative to the corresponding non-tapered diblock copolymers, with the inverse tapered materials showing the greatest deviation in TODT. Additionally, TODT was inversely related to the volume fraction of the tapered region in both normal and inverse tapered copolymer materials.

  19. Synthesis of Amylose-b-P2 VP Block Copolymers.

    PubMed

    Kumar, Kamlesh; Woortman, Albert J J; Loos, Katja

    2015-12-01

    A new class of rod-coil block copolymers is synthesized by chemoenzymatic polymerization. In the first step, maltoheptaose, which acts as a primer for the synthesis of amylose, is attached to poly(2-vinyl pyridine) (P2 VP). The enzymatic polymerization of maltoheptaose is carried out by phosphorylase to obtain amylose-b-P2 VP block copolymers. The block copolymer is characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and wide-angle X-ray scattering techniques. The designed molecules combine the inclusion complexation ability of amylose with the supramolecular complexation ability of P2 VP and therefore this kind of rod-coil block copolymers can be used to generate well-organized novel self-assembled structures. PMID:26437256

  20. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains

    PubMed Central

    Pollard, Benjamin

    2016-01-01

    Summary Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force–distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  1. Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains.

    PubMed

    Pollard, Benjamin; Raschke, Markus B

    2016-01-01

    Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force-distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

  2. Ionic Block Copolymers for Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Tsai, Tsung-Han; Herbst, Dan; Giffin, Guinevere A.; di Noto, Vito; Witten, Tom; Coughlin, E. Bryan

    2013-03-01

    Anion exchange membrane (AEM) fuel cells have regained interest because it allows the use of non-noble metal catalysts. Until now, most of the studies on AEM were based on random polyelectrolytes. In this work, Poly(vinylbenzyltrimethylammonium bromide)-b- (methylbutylene) ([PVBTMA][Br]-b-PMB) was studied by SAXS, TEM and dielectric spectroscopy to understand the fundamental structure-conductivity relationship of ion transport mechanisms within well-ordered block copolymers. The ionic conductivity and the formation of order structure were dependent on the casting solvent. Higher ion exchange capacity (IEC) of the membranes showed higher conductivity at as IEC values below 1.8mmol/g, as above this, the ionic conductivity decreases due to more water uptake leading to dilution of charge density. The humidity dependence of morphology exhibited the shifting of d-spacing to higher value and the alteration in higher characteristic peak of SAXS plot as the humidity increase from the dry to wet state. This phenomenon can be further explained by a newly developed polymer brush theory. Three ionic conduction pathways with different conduction mechanism within the membranes can be confirmed by broadband electric spectroscopy. US Army MURI (W911NF1010520)

  3. Orientation of Microdomains of Block Copolymers by Zone casting

    NASA Astrophysics Data System (ADS)

    Tang, Chuanbing; Matyjaszewski, Krzysztof; Kowalewski, Tomasz

    2007-03-01

    As a ``bottom up'' method, the self-assembly of block copolymers plays a vital role in the development of soft lithography for the fabrication of microelectronic devices. A variety of methods have been developed toward better and more precise controlled patterns on solid substrates. This presentation will describe a novel solution casting technique, ``zone casting'', to induce orientation of cylindrical and lamellar microphase-separated domains of various block copolymers.

  4. Self-doped microphase separated block copolymer electrolyte

    DOEpatents

    Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

    2002-01-01

    A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

  5. New adhesive systems based on functionalized block copolymers

    SciTech Connect

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.

    1997-05-01

    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  6. Preparation and Morphology of ABn Mictoarm Block Copolymers

    NASA Astrophysics Data System (ADS)

    Takano, Atsushi; Watanabe, Momoka; Asai, Yusuke; Suzuki, Jiro; Matsushita, Yushu

    A series of ABn mictoarm block copolymers (bottle brush copolymers) consisting of polystyrene (S) as a backbone and polyisoprenes (I) as grafts were precisely synthesized by an anionic polymerization, and their microphase-separated structures were investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering(SAXS). A copolymer with composition of φS =0.57 and number of grafts(n) of 10 shows characteristic cylindrical structure, where microdomains of S reveals hexagonal cross section with non-constant mean curvature interface. While a sample with composition of φS =0.37 and number of grafts(n) of 40 shows spherical structure with rather large S isolated domains and characteristic domain packing manner was found. Furthermore composition dependence of microphase-separated structures for SIn mictoarm block copolymers were investigated and compared to SI diblock copolymer system.

  7. Oligoaniline-containing supramolecular block copolymer nanodielectric materials.

    PubMed

    Hardy, Christopher G; Islam, Md Sayful; Gonzalez-Delozier, Dioni; Ploehn, Harry J; Tang, Chuanbing

    2012-05-14

    We report a new generation of nanodielectric energy storage materials based on supramolecular block copolymers. In our approach, highly polarizable, conducting nanodomains are embedded within an insulating matrix through block copolymer microphase separation. An applied electric field leads to electronic polarization of the conducting domains. The high interfacial area of microphase-separated domains amplifies the polarization, leading to high dielectric permittivity. Specifically, reversible addition fragmentation transfer (RAFT) polymerization was used to prepare block copolymers with poly(methyl acrylate) (PMA) as the insulating segment and a strongly acidic dopant moiety, poly-(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA), as the basis for the conducting segment. The PAMPSA block was complexed with an oligoaniline trimer to form a dopant-conjugated moiety complex that is electronically conductive after oxidation. For the undoped neat block copolymers, the increase of the PMA block length leads to a transition in dielectric properties from ionic conductor to dielectric capacitor with polarization resulting from migration of protons within the isolated PAMPSA domains. The oligoaniline-doped copolymers show remarkably different dielectric properties. At frequencies above 200 kHz, they exhibit characteristics of dielectric capacitors with much higher permittivity and lower dielectric loss than the corresponding undoped copolymers. PMID:22331602

  8. Stress induced topographic patterning in thin diblock copolymer films

    NASA Astrophysics Data System (ADS)

    Croll, Andrew; Crosby, Alfred

    2011-03-01

    When a thin rigid polymer film is attached to a soft elastic substrate and placed in a state of compressive stress, the system wrinkles as a critical stress is surpassed. This simple deformation pattern contains information about the mechanical state of both the polymer film and substrate. Although classical mechanics can be used to relate the global deformation of the film/substrate to the local wrinkle geometry as a function of materials properties, relatively little is known about how the thin capping film material accommodates the localized bending (and therefore localized stress). Here we conduct wrinkling experiments using a model diblock copolymer/elastomer composite. Wrinkling a homogeneous, disordered block copolymer film places the film in a well-defined initial stress state. When heated above its glass transition, the wrinkled film flows, microphase separates, and relaxes from the stress imposed by local wrinkle deformations. The periodic stress relaxation leads to the emergence of a new pattern in the microphase separated surface structure, thus providing new insight into how block copolymers react to stress.

  9. Electrically conductive doped block copolymer of polyacetylene and polyisoprene

    DOEpatents

    Aldissi, Mahmoud

    1985-01-01

    An electrically conductive block copolymer of polyisoprene and polyacetyl and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I.sub.2 to give it an electrical conductivity in the metallic regime.

  10. Using Tapered Block Copolymers to Create Conducting Nanomaterials

    NASA Astrophysics Data System (ADS)

    Epps, Thomas, III

    2014-03-01

    Soft materials, such as polymers, colloids, surfactants, and liquid crystals, are a technologically important class of matter employed in a variety of applications. One sub-class of soft material, block copolymers, provides the opportunity to design materials with attractive chemical and mechanical properties based on the ability to assemble into periodic structures with nanoscale domain spacings. Several applications for block copolymers currently under investigation in my group include battery and fuel cell membranes, analytical separations membranes, nano-tool templates, precursors to electronic arrays, and drug delivery vehicles. One area of recent progress in the group focuses on the behavior of conventional block copolymer and tapered block copolymer systems for lithium battery membrane applications. We find that we can tune poly(styrene- b-ethylene oxide) diblock copolymer nanostructures by adjusting the lithium counterion and lithium salt concentration, as well as the taper volume fraction and composition. Additionally, we can estimate the effective interaction parameters (χeff) for the salt-doped copolymers to determine the overall influence of tapering on the energetics of copolymer assembly. These tapered materials allow us to design nanostructured membrane systems with increased conductivity and improved mechanical properties in ion transport devices. We gratefully acknowledge AFOSR-PECASE (FA9550-09-1-0706) and NSF-CAREER (DMR-0645586) for financial support.

  11. Morphology and Proton Transport in Porous Block Copolymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    Chen, Chelsea; Kortright, Jeffrey; Wong, David; Balsara, Nitash

    2015-03-01

    Block copolymer electrolyte membranes consisting of a proton-conducting block and an uncharged structural block are attractive due to their potential in clean energy applications. Herein we demonstrate a novel approach of fabricating block copolymer electrolyte membranes, by inducing pores in the proton-conducting phase. We examine morphology of these membranes with contrast-matched resonant soft X-ray scattering (RSoXS) and electron tomography. Proton conductivity as a function of porosity and water activity is also investigated. By tuning the porosity of the membranes, we are able to adjust the water uptake of the membranes for improved proton conductivities, in both humid air and liquid water.

  12. Fracture of Semicrystalline-Glassy Block Copolymers: Chain Architecture Effects

    NASA Astrophysics Data System (ADS)

    Ryu, C. Y.; Fredrickson, G. H.; Kramer, E. J.; Hahn, S. F.

    2000-03-01

    We investigate the influence of chain architecture on the deformation and fracture of poly(vinylcyclohexane)-poly(ethylene) (PCHE-PE) block copolymers. Ordered thin films of PCHE-PE-PCHE (CEC) triblock and CECEC pentablock copolymers are bonded to ductile copper grids and deformed in tension and then examined by optical and transmission electron microscopy. Both PCHE homopolymer (M = 283,000 g/mol) and CEC triblock (M = 107,000 g/mol; fE =3D 0.29) undergo fracture via crazing followed by breakdown of crazes to form cracks producing catastrophic failure at a strain ɛ < 6%. The mechanism of deformation and the strain for catastrophic failure changes dramatically for CECEC. Deformation of the CECEC pentablock (M = 110,000 g/mol; fE = 0.29) takes place mainly by (shear) deformation zone formation. Shear deformation and crazing compete and the shear blunting of craze tips is frequently observed. The strain for the catastrophic failure increases in CECEC to ɛ > 30%, and breakdown of the deformed film occurs only locally. We attribute this change in deformation and failure mechanisms to the bridging chains within the C domains of CECEC.

  13. Block copolymer blends with improved oil absorption resistance

    SciTech Connect

    Himes, G.R.; Sanders, A.

    1989-11-14

    This patent describes a thermoplastic blend. It comprises: about 80 to about 20 parts by weight of an elastometric block copolymer having the general configuration A-B-A, wherein: each A block is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 4000 to about 115,000; the A blocks, in combination, comprise about 5 to about 35w% of the elastomeric block copolymer; and each B block is a non-hydrogenated butadiene hydrocarbon block consisting of 8 to 55 mole percent condensed butadiene units in the 1,2 configuration, or a hydrogenated butadiene hydrocarbon block consisting of 35 to 55 mole percent condensed butadiene units in the 1,2 configuration, and the B block has an average molecular weight of between about 20,000 and about 450,000; and about 20 to about 80 parts by weight of a block copolymer having the general configuration A-B-A wherein: each A block is a polymerized monoalkenyl aromatic hydrocarbon block having an average molecular weight of about 4000 to about 115,000; the A blocks, in combination, comprise about 5 to about 35 w % of the block copolymer; each B block is a polymerized butadiene hydrocarbon block consisting of about 18 to 34 mole percent condensed butadiene units in the 1,2 configuration, and the B block has an average molecular weight of between about 20,000 and about 450,000; and the B blocks are hydrogenated to an unsaturation that is less than about 5% of the original unsaturation.

  14. Effect of Film Thickness and Domain Spacing on Defect Densities in Directed Self-Assembly of Cylindrical Morphology Block Copolymers

    SciTech Connect

    Mishra, Vindhya; Fredrickson, Glenn H.; Kramer, Edward J.

    2012-04-30

    Directed assembly of block copolymer thin films is recognized as a high-throughput, low-cost complement to optical lithography with the ability to overcome the 32 nm natural resolution limit of conventional lithographic techniques. For bulk block copolymer systems, desired feature sizes ranging from 5 to 100 nm can be obtained by controlling the molecular weight and composition of a block copolymer, as long as the bulk order-disorder temperature (ODT) is such that the copolymer is well-segregated at the processing conditions. However, our studies on graphoepitaxially aligned cylindrical morphology block copolymer monolayer and bilayer films demonstrate that, as domain sizes are reduced, the block copolymer becomes increasingly susceptible to an unacceptably high density of thermally generated defects, resulting in a significant reduction of the ODT. Thus, in thin films, the minimum feature spacing accessible is limited by thermal defect generation and not by the bulk ODT. Our experimental studies on monolayer films of cylindrical morphology polystyrene-b-poly(2-vinyl pyridine) with microdomain spacings approaching 20 nm reveal that defect densities and the ODT are surprisingly sensitive to variations as small as 2 nm in the microdomain spacing. Additionally, the monolayer and bilayer ODT differ by nearly 100 C when the monolayer domain spacing is 20 nm, while the difference is only 20 C when the monolayer domain spacing is 22 nm. We explain this behavior using a quantitative estimation of the energetic cost of defect production in terms of the domain spacing, {chi}N, and block copolymer composition. These studies reveal unexpected consequences on the equilibrium defect densities of thin film block copolymers which must be accounted for when designing a block-copolymer-based directed-assembly process.

  15. Selective Semiconductor Nanocluster Deposition on Eptaxially Patterned Semicrystalline Block Copolymer Film

    NASA Astrophysics Data System (ADS)

    Park, Cheolmin; Lee, Jinwook; Jensen, Klavs F.; Bawendi, Moungi G.; Thomas, Edwin L.

    2001-03-01

    Monodisperse ZnS encapsulated CdSe semiconductor nanoclusters are sequestered in between the crystalline polyethylene (PE) lamellae of poly (ethylene-b-ethylene-alt-propylene-b ethylene) semicrystalline triblock copolymer epitaxially crystallized on single crystal of anthracene (AN). Epitaxy between PE block and An created a cross oriented texture of the edge-on crystalline PE lamellae in the thin film. At the same time, the nanoclusters, initially dissolved in the mixture of block copolymer and AN, were rejected out of the crystalline lamellae during epitaxial crystallization and selectively deposited in the amorphous region of the block copolymer. Selective distribution of nanoclusters on the cross oriented pattern structure is clearly evidenced by selected area diffraction (SAD) and bright field transmission electron microscope (TEM).

  16. Millisecond ordering of block-copolymer films via photo-thermal gradients

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2015-03-12

    For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photo-thermal gradients can be used to control the ordering of block-copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders-of-magnitude, compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block-copolymer film in less than a second. Finally, we provide examples of how control of the incident light-field can be used to generate prescribed configurations of block-copolymer nanoscale patterns.

  17. Millisecond ordering of block-copolymer films via photo-thermal gradients

    DOE PAGESBeta

    Majewski, Pawel W.; Yager, Kevin G.

    2015-03-12

    For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photo-thermal gradients can be used to control the ordering of block-copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders-of-magnitude, compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block-copolymer film in lessmore » than a second. Finally, we provide examples of how control of the incident light-field can be used to generate prescribed configurations of block-copolymer nanoscale patterns.« less

  18. Patterned silica films using microphase separation of a block copolymer

    NASA Astrophysics Data System (ADS)

    Kataoka, Sho; Takeuchi, Yasutaka; Endo, Akira

    2014-11-01

    Block copolymers exhibit various nanoscale ordered morphologies induced by microphase separation. Here, we present a method for providing two types of patterned silica films on Si wafer substrates simply by shifting the phase equilibrium of a block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-P4VP). In this method, siloxane is adsorbed onto poly(4-vinylpyridine) blocks of PS-P4VP whose structure varies with solvent polarity and is calcined to remove the block copolymer. Siloxane is in a dispersed phase with toluene as a solvent resulting in silica nanoparticle arrays, while siloxane is in a continuous phase with N, N-dimethylformamide (DMF) resulting in silica films with ordered mesopores. Since the pore size of silica films prepared in DMF is approximately 20 nm, the film has the ability to serve as a support for enzymes such as laccase.

  19. Fluorinated polyphenylenevinylene (PPV) block co-polymers for nanophotonics

    NASA Astrophysics Data System (ADS)

    Sun, Sam-Shajing; Nguyen, Thuong; Brooks, Jaleesa

    2013-09-01

    Polymer based optoelectronic materials and thin film devices exhibit great potential in future space applications due to their flexibility, light weight, large light absorption coefficient, and promising radiation tolerance in space environment as compared to their inorganic semiconductor counterparts. Since carbon-fluorine (C-F) chemical bonds are much stronger than the carbon-hydrogen (C-H) bonds, fluorinated polymer films offer great potential for space applications due their expected resistance to oxidation, thermal stability, excellent wear properties, and low coefficients of friction. Their use in a space environment is extremely attractive since they are expected to retain their lubricating characteristics in vacuum, unlike many solid lubricants. Current existing polymer photovoltaic materials and devices suffer low photoelectric power conversion efficiencies due to a number factors including poor morphologies at nano scale that hinder the charge separation and transport. This paper reports our recent work on a fluorinated DBfA type block copolymer system where the donor (D) block contains a donor substituted and hydrocarbon based polyphenylenevinylene (PPV), acceptor (fA) block contains a fluorinated and a sulfone acceptor substituted polyphenylenevinylene (f-PPV), and B is a non-conjugated and flexible bridge unit. Preliminary studies reveal DBfA exhibits better nano phase morphologies and over 100 times more efficient optoelectronic conversion efficiencies as compared to D/fA blend.

  20. Using click chemistry to modify block copolymers and their morphologies

    NASA Astrophysics Data System (ADS)

    Wollbold, Johannes

    Microphase separated block copolymers (BCPs) are emerging as promising templates and scaffolds for the fabrication of nanostructured materials. To achieve the desired nanostructures, it is necessary to establish convenient approaches to control the morphology of BCPs. It remains challenging to induce morphological transitions of BCPs via external fields. Click chemistry, especially alkyne/azide click chemistry, has been widely used to synthesize novel functionalized materials. Here, we demonstrate that alkyne/azide click chemistry can be used as an efficient approach to chemically modify BCPs and therefore induce morphological transitions. Alkyne-functionalized diblock copolymers (di-BCPs) poly(ethylene oxide)- block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) have been successfully synthesized. When the di-BCP is blended with an azide additive Rhodamine B azide and annealed at elevated temperatures, click reaction occurs between the two components. With the Rhodamine B structure attached to the polymer backbone, the di-BCP shows dramatic change in the interactions between the two blocks and the volume fraction of each block. As a result, morphological transitions, such as disorder-to-order transitions (DOTs) and order-to-order transitions (OOTs), are observed. The reaction kinetics and morphology evolution during the click chemistry induced DOTs have been investigated by in-situ and ex-situ characterizations, and fast kinetics properties are observed. Microphase separated morphologies after the DOTs or OOTs are dictated by the composition of neat di-BCPs and the mole ratio between the alkyne and azide groups. The DOTs of PEO-b-P(nBMA-r-PgMA) di-BCPs induced by alkyne/azide click chemistry have also been achieved in thin film geometries, with comparable kinetics to bulk samples. The orientation of the microdomains is dependent on the grafting density of Rhodamine B structure as well as film thickness. At higher grafting densities

  1. Design of nanostructured materials from block copolymer self-assembly

    NASA Astrophysics Data System (ADS)

    Leolukman, Melvina

    We present two classes of nanostructured materials by combining the self assembly of block copolymer (BCP) with suitable small molecule chemistry, which are applicable to organic electro-optics (EO) and as etch-resistant masks for nanofabrication. The underlying principles of designing the specific interactions between BCP host and guest molecules, driving the self-assembly in bulk and thin film, and dictating domain orientation are concepts common to both of these areas. Nanostructured EO materials were created by selectively encapsulating EO chromophores by hydrogen-bonding to the pyridine groups of a linear-diblock copolymer (linear-diBCP) namely polystyrene-block-poly(4-vinyl pyridine) [PS-b-P4VP], or a linear-dendritic-BCP. With the linear-diBCP host, we discovered that poled order in confined domains depends on domain shape, chromophore concentration within the domain, and thermal history. The linear-dendritic-BCP is an excellent host as it efficiently disperses the chromophores into small domains (5-10nm), and keeps the chromophores apart within the domains due to the dendritic architecture. These morphological effects translated into excellent film processability, increased chromophore loading, and two-fold enhancements in the EO coefficient (r 33) when compared to a corresponding homopolymer system. A new class of organic-inorganic nanostructured materials based on polyhedral oligomeric silsesquioxane (POSS) was synthesized as a passive template for pattern transfer. We developed a living anionic polymerization route for methacrylate-functionalized POSS and synthesized two kinds of BCPs, namely PS-b-PMAPOSS and PMMA-b-PMAPOSS. The anionic route allows high degree of polymerization, narrow polydispersity, and tunable POSS block length. These lead to well defined spherical, cylindrical, and lamellar morphologies, as well as formation of hierarchical structures upon thermal annealing. Both POSS-containing BCPs were assembled in thin film and converted to hard

  2. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there

  3. Formation and structural properties of multi-block copolymer vesicles

    NASA Astrophysics Data System (ADS)

    Wang, Rong; Ma, Shiying

    2014-03-01

    Due to the unique structure, vesicles have attracted considerable attention for their potential applications, such as gene and drug delivery, microcapsules, nanoreactors, cell membrane mimetic, synthetic organelles, etc. By using dissipative particle dynamics, we studied the self-assembly of amphiphilic multi-block copolymer. The phase diagram was constructed by varying the interaction parameters and the composition of the block copolymers. The results show that the vesicles are stable in a large region which is different from the diblock copolymer or triblock copolymer. The structural properties of vesicles can be controlled by varying the interaction parameters and the length of the hydrophobic block. The relationship between the hydrophilic and hydrophobic block length vs the aqueous cavity size and vesicle size are revealed. The copolymers with shorter hydrophobic blocks length or the higher hydrophilicity are more likely to form vesicles with larger aqueous cavity size and vesicle size as well as thinner wall thickness. However, the increase in hydrophobic-block length results to form vesicles with smaller aqueous cavity size and larger vesicle size. Acknowledgments. This work has been supported by NNSFC (No. 21074053) and NBRPC (No. 2010CB923303).

  4. Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment

    SciTech Connect

    Liedel, Clemens; Pester, Christian; Ruppel, Markus A; Lewin, Christian; Pavan, Mariela J.; Urban, Volker S; Shenhar, Roy; Bosecke, Peter; Boker, Alexander

    2013-01-01

    We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-block-poly(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment.

  5. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, M.S.; Saunders, R.

    1997-02-18

    Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

  6. Morphology of Novel Semicrystalline Ethylene-α-Olefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Register, Richard; Landes, Brian

    2009-03-01

    In semicrystalline block copolymers, the solid-state structure can be set either by block incompatibility or by crystallization of one or more blocks. Depending on the block interaction strength, a wide array of solid-state morphologies may be observed, ranging from spherulitic to confined crystallization within preexisting microphase-separated domains. Dow Chemical has recently developed a novel chain shuttling polymerization process to produce olefin block copolymers with alternating amorphous and semicrystalline chain segments, where each block exhibits the most-probable distribution. We examined the melt and solid-state morphologies of these novel olefin block copolymers, having a high octene content in the amorphous block, using two- dimensional synchrotron small-angle and wide-angle x-ray scattering on specimens oriented by channel die compression. Multiblock and diblock copolymers with near-symmetric compositions showed well-ordered lamellar structures at room temperature with long periods exceeding 100 nm, with little dependence on thermal history, indicating the presence of a mesophase-separated melt which templates crystallization.

  7. Ion and temperature sensitive polypeptide block copolymer.

    PubMed

    Joo, Jae Hee; Ko, Du Young; Moon, Hyo Jung; Shinde, Usha Pramod; Park, Min Hee; Jeong, Byeongmoon

    2014-10-13

    A poly(ethylene glycol)/poly(L-alanine) multiblock copolymer incorporating ethylene diamine tetraacetic acid ([PA-PEG-PA-EDTA(m)) was synthesized as an ion/temperature dual stimuli-sensitive polymer, where the effect of different metal ions (Cu(2+), Zn(2+), and Ca(2+)) on the thermogelation of the polymer aqueous solution was investigated. The dissociation constants between the metal ions and the multiblock copolymer were calculated to be 1.2 × 10(-7), 6.6 × 10(-6), and 1.2 × 10(-4) M for Cu(2+), Zn(2+), and Ca(2+), respectively, implying that the binding affinity of the multiblock copolymer for Cu(2+) is much greater than that for Zn(2+) or Ca(2+). Atomic force microscopy and dynamic light scattering of the multiblock copolymer containing metal ions suggested micelle formation at low temperature, which aggregated as the temperature increased. Circular dichroism spectra suggested that changes in the α-helical secondary structure of the multiblock copolymer were more pronounced by adding Cu(2+) than other metal ions. The thermogelation of the multiblock copolymer aqueous solution containing Cu(2+) was observed at a lower temperature, and the modulus of the gel was significantly higher than that of the system containing Ca(2+) or Zn(2+), in spite of the same concentration of the metal ions and their same ionic valence of +2. The above results suggested that strong ionic complexes between Cu(2+) and the multiblock copolymer not only affected the secondary structure of the polymer but also facilitated the thermogelation of the polymer aqueous solution through effective salt-bridge formation even in a millimolar range of the metal ion concentration. Therefore, binding affinity of metal ions for polymers should be considered first in designing an effective ion/temperature dual stimuli-sensitive polymer. PMID:25178662

  8. Highly conductive side chain block copolymer anion exchange membranes.

    PubMed

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days. PMID:27216558

  9. Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

    SciTech Connect

    Russell, Thomas P.; Hong, Sung Woo; Lee, Doug Hyun; Park, Soojin; Xu, Ting

    2015-10-13

    A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

  10. Radical-cured block copolymer-modified thermosets

    SciTech Connect

    Redline, Erica M.; Francis, Lorraine F.; Bates, Frank S.

    2013-01-10

    Poly(ethylene-alt-propylene)-b-poly(ethylene oxide) (PEP-PEO) diblock copolymers were synthesized and added at 4 wt % to 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BisGMA), a monomer that cures using free radical chemistry. In separate experiments, poly(ethylene glycol) dimethacrylate (PEGDMA) was combined as a secondary monomer with BisGMA and the monomers were loaded with 4 wt % PEP-PEO. The diblock copolymers self-assembled into well-dispersed spherical micelles with PEP cores and PEO coronas. No appreciable change in the final extent of cure of the thermosets was caused by the addition of diblock copolymer, except in the case of BisGMA, where the addition of the block copolymer increased extent of cure by 12%. Furthermore, the extent of cure was increased by 29% and 37% with the addition of 25 and 50 wt % PEGDMA, respectively. Elastic modulus and fracture resistance were also determined, and the values indicate that the addition of block copolymers does not significantly toughen the thermoset materials. This finding is surprising when compared with the large increase in fracture resistance seen in block copolymer-modified epoxies, and an explanation is proposed.

  11. Single- and Multilayered Nanostructures via Laser-Induced Block Copolymer Self-Assembly

    NASA Astrophysics Data System (ADS)

    Majewski, Pawel; Yager, Kevin; Rahman, Atikur; Black, Charles

    We present a novel method of accelerated self-assembly of block copolymer thin films utilizing laser light, called Laser Zone Annealing (LZA). In our approach, steep temperature transients are induced in block copolymer films by rastering narrowly focused laser line over the light-absorbing substrate. Extremely steep temperature gradients accelerate the process of self-assembly by several orders-of-magnitude compared to conventional oven annealing, and, when coupled to photo-thermal shearing, lead to global alignment of block copolymer domains assessed by GISXAS diffraction studies and real-space SEM imaging. We demonstrate monolithic alignment of various block-copolymer thin films including PS-b-PMMA, PS-b-PEO, PS-b-P2VP, PS-b-PI and observe different responsiveness to the shearing rate depending on the characteristic relaxation timescale of the particular material. Subsequently, we use the aligned polymeric films as templates for synthesis of single- and multi-layered arrays of inorganic, metallic or semiconducting nanowires and nanomeshes and investigate their anisotropic electro-optical properties. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

  12. Manipulating Interfaces through Surface Confinement of Poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone), a Dually Reactive Block Copolymer

    SciTech Connect

    Lokitz, Bradley S; Wei, Jifeng; Hinestrosa Salazar, Juan P; Ivanov, Ilia N; Browning, James B; Ankner, John Francis; Kilbey, II, S Michael; Messman, Jamie M

    2012-01-01

    The assembly of dually reactive, well-defined diblock copolymers incorporating the chemoselective/functional monomer, 4,4-dimethyl-2-vinylazlactone (VDMA) and the surface-reactive monomer glycidyl methacrylate (GMA) is examined to understand how competition between surface attachment and microphase segregation influences interfacial structure. Reaction of the PGMA block with surface hydroxyl groups not only anchors the copolymer to the surface, but limits chain mobility, creating brush-like structures comprising PVDMA blocks, which contain reactive azlactone groups. The block copolymers are spin coated at various solution concentrations and annealed at elevated temperature to optimize film deposition to achieve a molecularly uniform layer. The thickness and structure of the polymer thin films are investigated by ellipsometry, infrared spectroscopy, and neutron reflectometry. The results show that deposition of PGMA-b-PVDMA provides a useful route to control film thickness while preserving azlactone groups that can be further modified with biotin-poly(ethylene glycol)amine to generate designer surfaces. The method described herein offers guidance for creating highly functional surfaces, films, or coatings through the use of dually reactive block copolymers and postpolymerization modification.

  13. Dynamic response of block copolymer wormlike micelles to shear flow

    NASA Astrophysics Data System (ADS)

    Lonetti, B.; Kohlbrecher, J.; Willner, L.; Dhont, J. K. G.; Lettinga, M. P.

    2008-10-01

    The linear and nonlinear dynamic response to an oscillatory shear flow of giant wormlike micelles consisting of Pb-Peo block copolymers is studied by means of Fourier transform rheology. Experiments are performed in the vicinity of the isotropic-nematic phase transition concentration, where the location of isotropic-nematic phase transition lines is determined independently. Strong shear-thinning behaviour is observed due to critical slowing down of orientational diffusion as a result of the vicinity of the isotropic-nematic spinodal. This severe shear-thinning behaviour is shown to result in gradient shear banding. Time-resolved small-angle neutron scattering experiments are used to obtain an insight into the microscopic phenomena that underlie the observed rheological response. An equation of motion for the order parameter tensor and an expression of the stress tensor in terms of the order parameter tensor are used to interpret the experimental data, both in the linear and nonlinear regimes. Scaling of the dynamic behaviour of the orientational order parameter and the stress is found when critical slowing down due to the vicinity of the isotropic-nematic spinodal is accounted for.

  14. Host-guest self-assembly in block copolymer blends.

    PubMed

    Park, Woon Ik; Kim, Yongjoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L; Alexander-Katz, Alfredo; Jung, Yeon Sik

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs. PMID:24217036

  15. Host-Guest Self-assembly in Block Copolymer Blends

    PubMed Central

    Park, Woon Ik; Kim, YongJoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L.; Alexander-Katz, Alfredo; Jung, Yeon Sik

    2013-01-01

    Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs. PMID:24217036

  16. Self-Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra- to Nanofiltration.

    PubMed

    Yu, Haizhou; Qiu, Xiaoyan; Moreno, Nicolas; Ma, Zengwei; Calo, Victor Manuel; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2015-11-16

    The self-assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra- to nanofiltration and decrease the pore size of self-assembled block copolymer membranes to below 5 nm without post-treatment. It is now reported that the self-assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol(-1) in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux. PMID:26388216

  17. Characterization of Lithium Polysulfide Salts in Homopolymers and Block Copolymers

    NASA Astrophysics Data System (ADS)

    Wang, Dunyang; Wujcik, Kevin; Balsara, Nitash

    Ion-conducting polymers are important for solid-state batteries due to the promise of better safety and the potential to produce higher energy density batteries. Nanostructured block copolymer electrolytes can provide high ionic conductivity and mechanical strength through microphase separation. One of the potential use of block copolymer electrolytes is in lithium-sulfur batteries, a system that has high theoretical energy density wherein the reduction of sulfur leads to the formation of lithium polysulfide intermediates. In this study we investigate the effect of block copolymer morphology on the speciation and transport properties of the polysulfides. The morphology and conductivities of polystyrene-b-poly(ethylene oxide) (SEO) containing lithium polysulfides were studies using small-angle X-ray scattering and ac impedance spectroscopy. UV-vis spectroscopy is being used to determine nature of the polysulfide species in poly(ethylene oxide) and SEO. Department of Energy, Soft Matter Electron Microscopy Program and Battery Materials Research Program.

  18. Liquid-crystalline ordering helps block copolymer self-assembly.

    PubMed

    Yu, Haifeng; Kobayashi, Takaomi; Yang, Huai

    2011-08-01

    Interaction between liquid-crystalline elastic deformation and microphase separation in liquid-crystalline block copolymers enables them to supramolecularly assemble into ordered nanostructures with high regularity. With the help of liquid-crystalline alignment, parallel and perpendicular patterning of nanostructures is fabricated with excellent reproducibility and mass production, which provides nanotemplates and nanofabrication processes for preparing varieties of nanomaterials. Furthermore, nanoscale microphase separation improves the optical performance of block-copolymer fi lms by eliminating the scattering of visible light, leading to advanced applications in optical devices and actuators. Recent progress in liquid-crystalline block copolymers, including their phase diagram, structure-property relationship, nanostructure control and nanotemplate applications, is reviewed. PMID:21910267

  19. Controlling block copolymer phase behavior using ionic surfactant

    NASA Astrophysics Data System (ADS)

    Ray, D.; Aswal, V. K.

    2016-05-01

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO26PO39EO26)] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle-surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  20. Amphiphilic block copolymer nanocontainers as bioreactors

    NASA Astrophysics Data System (ADS)

    Nardin, C.; Widmer, J.; Winterhalter, M.; Meier, W.

    2001-04-01

    Self-assembly of an amphiphilic triblock copolymer carrying polymerizable end-groups is used to prepare nanometer-sized vesicular structures in aqueous solution. The triblock copolymer shells of the vesicles can be regarded as a mimetic of biological membranes although they are 2 to 3 times thicker than a conventional lipid bilayer. Nevertheless, they can serve as a matrix for membrane-spanning proteins. Surprisingly, the proteins remain functional despite the extreme thickness of the membranes and that even after polymerization of the reactive triblock copolymers. This opens a new field to create mechanically stable protein/polymer hybrid membranes. As a representative example we functionalize (polymerized) triblock copolymer vesicles by reconstituting a channel-forming protein from the outer cell wall of Gram-negative bacteria. The protein used (OmpF) acts as a size-selective filter, which allows only for passage of molecules with a molecular weight below 400 g mol^{-1}. Therefore substrates may still have access to enzymes encapsulated in such protein/polymer hybrid nanocontainers. We demonstrate this using the enzyme β -lactamase which is able to hydrolyze the antibiotic ampicillin. In addition, a transmembrane voltage above a given threshold causes a reversible gating transition of OmpF. This can be used to reversibly activate or deactivate the resulting nanoreactors.

  1. Quasi-Block Copolymers Based on a General Polymeric Chain Stopper.

    PubMed

    Sanguramath, Rajashekharayya A; Nealey, Paul F; Shenhar, Roy

    2016-07-11

    Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a "chain stopper" functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3 Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3 Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials. PMID:27276387

  2. Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

    DOE PAGESBeta

    Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; Yager, Kevin G.; Strzalka, Joseph; Nie, Wanyi; Mohite, Aditya D.; Verduzco, Rafael

    2015-11-03

    All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor-block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we show thatmore » the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

  3. Self-Assembly of a Selectively Modified Fluorinated Block Copolymer

    NASA Astrophysics Data System (ADS)

    Davidock, Drew; Hillmyer, Marc; Lodge, Timothy

    2002-03-01

    Selective modification can be used to systematically tune the strength of the thermodynamic interaction between the two segments of a block copolymer. It also offers an effective method for the preparation of model fluorinated block copolymers, which are difficult to synthesize directly. In this study, the effect of controlled difluorocarbene (CF_2) addition to the polyisoprene block on the self-assembly of a series of poly(ethylethylene)-b-polyisoprene (PEE-b-PI) copolymers was investigated. Equilibrium morphologies were determined by small-angle X-ray scattering (SAXS). An effective interaction parameter (\\chi_eff) between the PEE and FPI-s-PI was calculated from the domain spacing, and is found to increase by a factor of ~400 upon complete CF2 modification. The resulting materials also offer an opportunity to examine the phase behavior all the way from weak to strong segregation with one parent copolymer. Using a binary interaction model originally developed for homopolymer/copolymer blends, we were able to model the dependence of \\chi_eff on the extent of fluorination in a quantitative manner and obtain values for the three pairwise interaction parameters.

  4. Block and Graft Copolymers of Polyhydroxyalkanoates

    NASA Astrophysics Data System (ADS)

    Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

    2004-03-01

    Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

  5. Chain exchange kinetics of block copolymer micelles in ionic liquids

    NASA Astrophysics Data System (ADS)

    Ma, Yuanchi; Lodge, Timothy

    The chain exchange kinetics of block copolymer micelles has been studied using time-resolved small-angle neutron scattering (TR-SANS), a key tool in determining the average micelle composition in contrast-matched solvents. In this work, PMMA-block-PnBMA was selected as the model block copolymer, which has a LCST behavior in the common ionic liquids, [EMIM][TFSI] and [BMIM][TFSI]. We examined the chain exchange kinetics of three PMMA-block-PnBMA copolymers, with identical PMMA block length (MPMMA = 25000) and different PnBMA block lengths (MPnBMA = 24000, 35000 and 53000); the Flory-Huggins interaction parameter (χ) between the core (PnBMA) and the solvent were varied by mixing [EMIM][TFSI] and [BMIM][TFSI] in different ratios. We found that the relaxation of the initial segregation of h- and d- micelles followed the same form with the time as previously developed by our group. Assuming that single chain expulsion is the rate limiting step, the thermal barrier was found to depend linearly on the core block length (Ncore) . Furthermore, the effect of χ on the chain exchange kinetics will also be discussed.

  6. Yield Stress Enhancement in Glassy-Polyethylene Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Polyethylene (PE) has the highest annual production volume of all synthetic polymers worldwide, and is valuable across many applications due to its low cost, toughness, processability, and chemical resistance. However, PE is not well suited to certain applications due to its modest yield stress and Young's modulus (approximately 30 MPa and 1 GPa, respectively for linear, high-density PE). Irreversible deformation of PE results from dislocation of crystal stems and eventual crystal fragmentation under applied stress. The liquid-like amorphous fraction provides no useful mechanical support to the crystal fold surface in a PE homopolymer, so the only method to enhance the force required for crystal slip, and hence the yield stress, is crystal thickening via thermal treatment. An alternative route towards modifying the mechanical properties of PE involves copolymerization of a minority high-glass transition temperature block into a majority-PE block copolymer. In this work, we investigate a system of glassy/linear-PE block copolymers prepared via ring-opening metathesis polymerization of cyclopentene and substituted norbornene monomers followed by hydrogenation. We demonstrate that a large change in mechanical properties can be achieved with the addition of a short glassy block (e.g. a doubling of the yield stress and Young's modulus versus PE homopolymer with the addition of 25 percent glassy block). Furthermore, owing to the low interaction energy between PE and the substituted polynorbornene blocks employed, these high-yield PE block copolymers can exhibit single-phase melts for ease of processability.

  7. Modeling Line Edge Roughness in Lamellar Block Copolymer Systems

    NASA Astrophysics Data System (ADS)

    Patrone, Paul; Gallatin, Gregg

    2012-02-01

    Block copolymers offer an appealing alternative to current lithographic techniques with regard to fabrication of the next generation microprocessors. However, if copolymers are to be useful on an industrial manufacturing scale, they must meet or exceed lithography specifications for placement and line edge roughness (LER) of resist features. Here we discuss a field theoretic approach to modeling the LER in the lamellar phase of a strongly segregated block copolymer system. Our model is based on the Leibler-Ohta-Kawasaki free energy functional, which takes the Flory-Huggins parameter and index of polymerization as inputs. We consider a domain with a finite number of phase separated microdomains; at the system boundary, we apply conditions akin to a chemical pinning field. Using a path integral formalism, we determine how fluctuations of the microdomain boundaries depend on distance from the system boundary, number of microdomains, the Flory-Huggins parameter, and index of polymerization.

  8. Block Copolymer Membranes for Efficient Capture of a Chemotherapy Drug

    PubMed Central

    2016-01-01

    We introduce the use of block copolymer membranes for an emerging application, “drug capture”. The polymer is incorporated in a new class of biomedical devices, referred to as ChemoFilter, which is an image-guided temporarily deployable endovascular device designed to increase the efficacy of chemotherapy-based cancer treatment. We show that block copolymer membranes consisting of functional sulfonated polystyrene end blocks and a structural polyethylene middle block (S-SES) are capable of capturing doxorubicin, a chemotherapy drug. We focus on the relationship between morphology of the membrane in the ChemoFilter device and efficacy of doxorubicin capture measured in vitro. Using small-angle X-ray scattering and cryogenic scanning transmission electron microscopy, we discovered that rapid doxorubicin capture is associated with the presence of water-rich channels in the lamellar-forming S-SES membranes in aqueous environment. PMID:27547493

  9. Development of block co-polymers as self-assembling templates for patterned media.

    SciTech Connect

    Warke, V.; Bakker, M. G.; Hong, K.; Mays, J.; Britt, P.; Li, X.; Wang, J.; X-Ray Science Division; Univ. of Alabama; ORNL

    2006-01-01

    Block copolymers that self-organize are of interest as templates for patterned media, as they potentially provide a low cost fabrication route. Poly(styrene)-Poly(methylmethacrylate) block co-polymers (PS-b-PMMA) of appropriate block length and PS to PMMA ratio self-assemble into a 2-D hexagonal phase in which the PS majority phase is continuous and surrounds cylinders of the minority, PMMA phase. For application of this phase to patterned media it is necessary that the cylinders of the minority phase be oriented perpendicular to the substrate surface. This can be achieved by a number of methods, including appropriate choice of substrate and use of a random co-polymer underlayer. Appropriate substrates include H-terminated silicon, some carbon coatings and some ITO glasses. Use of an acetic acid wash causes the minority PMMA component can be induced to be rearranged, giving rise to pores perpendicular to the substrate. Electrodeposition of a metal into the pores produces a hardmask which can be used with ion-milling to transfer the block co-polymer pattern onto a magnetic thin film.

  10. Direct Immersion Solvent Annealing of Nano-filled Block Copolymer Films

    NASA Astrophysics Data System (ADS)

    Longanecker, Melanie; Modi, Arvind; Yuan, Guangcui; Satija, Sushil; Bang, Joona; Karim, Alamgir; University of Akron Team; National Institute of Technology Collaboration; Korea University Collaboration

    The addition of nanoparticles to polymer films is a strategic approach to enhance film properties such as optical, thermal, hardness, conductivity, permeability etc. with inorganic components while maintaining an easily processable polymer matrix. To this end, the ``annealing'' of block copolymers while immersed directly in a chamber of solvent is examined to determine its efficacy in ordering nano-filled block copolymer films. Previously we have shown that it is possible to order neat block copolymer films in a mixture of solvents, and this research follows up that work. Specifically, we observe and utilize the effects of direct immersion solvent annealing (DIA) on lamellar poly(styrene-b-methyl methacrylate) thin films with loadings of gold nanoparticles as high as 25 percent by mass. Neutron reflection confirms that DIA is a viable technique applicable to ordering these highly loaded, nano-filled block copolymer systems. Some notable differences exist with respect to results on conservation of domain spacing that may be beneficial to film barrier properties, accomplished with minimal disruption of order and fast kinetics that is compatible with roll-to-roll techniques.

  11. Hierarchical pattern formation through photo-induced disorder in block copolymer/additive composite films

    NASA Astrophysics Data System (ADS)

    Yao, Li; Watkins, James

    2013-03-01

    Segregation strength in hybrid materials can be increased through selective hydrogen bonding between organic or nanoparticle additives and one block of weakly segregated block copolymers to generate well ordered hybrid materials. Here, we report the use of enantiopure tartaric acid as the additive to dramatically improve ordering in poly(ethylene oxide-block-tert-butyl acrylate) (PEO-b-PtBA) copolymers. Phase behavior and morphologies within both bulk and thin films were studied by TEM, AFM and X-ray scattering. Suppression of PEO crystallization by the interaction between tartaric acid and the PEO block enables the formation of well ordered smooth thin films. With the addition of a photo acid generator, photo-induced disorder in PEO-b-PtBA/tartaric acid composite system can be achieved upon UV exposure to deprotect PtBA block to yield poly(acrylic acid) (PAA), which is phase-miscible with PEO. Due to the strong interaction of tartaric acid with both blocks, the system undergoes a disordering transition within seconds during a post-exposure baking. With the assistance of trace-amounts of base quencher, high resolution, hierarchical patterns of sub-micron regions of ordered and disordered domains were achieved in thin films through area-selective UV exposure using a photo-mask. Funding from Center for Hierarchical Manufacturing (CHM); Facility support from Materials Research Science and Engineering Center at UMass Amherst and Cornell High Energy Synchrotron Source

  12. Fast assembly of ordered block copolymer nanostructures through microwave annealing.

    PubMed

    Zhang, Xiaojiang; Harris, Kenneth D; Wu, Nathanael L Y; Murphy, Jeffrey N; Buriak, Jillian M

    2010-11-23

    Block copolymer self-assembly is an innovative technology capable of patterning technologically relevant substrates with nanoscale precision for a range of applications from integrated circuit fabrication to tissue interfacing, for example. In this article, we demonstrate a microwave-based method of rapidly inducing order in block copolymer structures. The technique involves the usage of a commercial microwave reactor to anneal block copolymer films in the presence of appropriate solvents, and we explore the effect of various parameters over the polymer assembly speed and defect density. The approach is applied to the commonly used poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) and poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) families of block copolymers, and it is found that the substrate resistivity, solvent environment, and anneal temperature all critically influence the self-assembly process. For selected systems, highly ordered patterns were achieved in less than 3 min. In addition, we establish the compatibility of the technique with directed assembly by graphoepitaxy. PMID:20964379

  13. Order and Disorder in Polydisperse Block Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Lynd, Nathaniel; Hillmyer, Marc

    2007-03-01

    Utilizing creative strategies for the synthesis of model controlled-polydispersity poly(ethylene-alt-propylene)-b-poly(d,l-lactide)(PEP-PLA) and polystyrene-b-polyisoprene(PS-PI) block copolymers, the effects of increased breadth in the molecular weight distribution on block copolymer self-assembly were investigated. Small-angle x-ray scattering and rheological measurements were carried out to characterize the morphological details of these self-assembled materials as a function of their polydispersity, interaction strengths, and compositions. A number of surprising consequences of increased breadth in the molecular weight distribution emerged; the domain spacing of the ordered structures increased, changes in morphology occurred, and the degree of segregation at the order-disorder transitions changed as well, particularly for asymmetric block copolymers. The change in the degree of segregation at the order-disorder transition as the polydispersity was increased was found to be dependent on the block copolymer composition, e.g., for PEP-PLA and PS-PI at asymmetric compositions, when the polydispersity was increased in the minority component, the degree of segregation at the order-disorder transition decreased, whereas when the polydispersity was increased in the majority component, the degree of segregation at the order-disorder transition increased.

  14. Linear-dendritic block copolymer for drug and gene delivery.

    PubMed

    Fan, Xiaohui; Zhao, Yanli; Xu, Wei; Li, Lingbing

    2016-05-01

    Dendrimers as a new class of polymeric materials have a highly ordered branched structure, exact molecular weight, multivalency and available internal cavities, which make them extensively used in biology and drug-delivery. Concurrent with the development of dendrimers, much more attention is drawn to a novel block copolymer which combines linear chains with dendritic macromolecules, the linear-dendritic block copolymer (LDBC). Because of the different solubility of the contrasting regions, the amphiphilic LDBCs could self-assemble to form aggregates with special core-shell structures which exhibit excellent properties different from traditional micelles, such as lower critical micelle concentration, prolonged circulation in the bloodstream, better biocompatibility, and lower toxicity. The present review briefly describes the type of LDBC, the self-assembly behavior in solution, and the application in delivery system including the application as drug carriers and gene vectors. The interactions between block copolymers and drugs are also summarized to better understand the release mechanism of drugs from the linear-dendritic block copolymers. PMID:26952501

  15. Electrical biomolecule detection using nanopatterned silicon via block copolymer lithography.

    PubMed

    Jeong, Chang Kyu; Jin, Hyeong Min; Ahn, Jae-Hyuk; Park, Tae Jung; Yoo, Hyeon Gyun; Koo, Min; Choi, Yang-Kyu; Kim, Sang Ouk; Lee, Keon Jae

    2014-01-29

    An electrical biosensor exploiting a nanostructured semiconductor is a promising technology for the highly sensitive, label-free detection of biomolecules via a straightforward electronic signal. The facile and scalable production of a nanopatterned electrical silicon biosensor by block copolymer (BCP) nano-lithography is reported. A cost-effective and large-area nanofabrication, based on BCP self-assembly and single-step dry etching, is developed for the hexagonal nanohole patterning of thin silicon films. The resultant nanopatterned electrical channel modified with biotin molecules successfully detects the two proteins, streptavidin and avidin, down to nanoscale molarities (≈1 nm). The nanoscale pattern comparable to the Debye screening length and the large surface area of the three-dimensional silicon nanochannel enable excellent sensitivity and stability. A device simulation confirms that the nanopatterned structure used in this work is effective for biomolecule detection. This approach relying on the scalable self-assembly principle offers a high-throughput manufacturing process for clinical lab-on-a-chip diagnoses and relevant biomolecular studies. PMID:23881835

  16. Square Grains in Asymmetric Rod-Coil Block Copolymers

    SciTech Connect

    Olsen, B.D.; Toney, M.F.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley /SLAC, SSRL

    2009-04-30

    Unlike the rounded grains that are well known to form in most soft materials, square grains of microphase-separated lamellae are observed in thin films of a rod-coil block copolymer because of hierarchical structuring originating from the molecular packing of the rods. The square grains are oriented with lamellar layers parallel to the film interface and result from growth along orthogonal low-surface-energy directions as a result of the effects of the tetragonal crystalline lattice that forms within the rod-rich lamellar nanodomains of poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylene vinylene)-b-polyisoprene (PPV-b-PI). These grain shapes form only for a narrow range of coil volume fractions around 72% as a result of kinetic barriers at lower coil fractions and disordering of the lattice at higher coil fractions, and the polydisperse grain size suggests that growth is nucleation-limited. The grains form in both weakly and moderately segregated polymers at all annealing temperatures below the order-disorder transition, and they are observed for all thicknesses at which parallel-oriented grains are grown.

  17. Fluctuation Dynamics of Block Copolymer Vesicles

    SciTech Connect

    Falus, P.; Borthwick, M.A.; Mochrie, S.G.J.

    2010-07-13

    X-ray photon correlation spectroscopy was used to characterize the wave-vector- and temperature-dependent dynamics of spontaneous thermal fluctuations in a vesicle (L4) phase that occurs in a blend of a symmetric poly(styrene-ethylene/butylene-styrene) triblock copolymer with a polystyrene homopolymer. Measurements of the intermediate scattering function reveal stretched-exponential behavior versus time, with a stretching exponent slightly larger than 2/3. The corresponding relaxation rates show an approximate q{sup 3} dependence versus wave vector. Overall, the experimental measurements are well described by theories that treat the dynamics of independent membrane plaquettes.

  18. A route to nanoscopic materials via seeded sequential infiltration synthesis on block copolymer templates.

    SciTech Connect

    Peng, Q.; Tseng, Y.-C.; Darling, S. B.; Elam, J. W.

    2011-06-01

    Sequential infiltration synthesis (SIS), combining stepwise molecular assembly reactions with self-assembled block copolymer (BCP) substrates, provides a new strategy to pattern nanoscopic materials in a controllable way. The selective reaction of a metal precursor with one of the pristine BCP domains is the key step in the SIS process. Here we present a straightforward strategy to selectively modify self-assembled polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP thin films to enable the SIS of a variety of materials including SiO{sub 2}, ZnO, and W. The selective and controlled interaction of trimethyl aluminum with carbonyl groups in the PMMA polymer domains generates Al-CH{sub 3}/Al-OH sites inside the BCP scaffold which can seed the subsequent growth of a diverse range of materials without requiring complex block copolymer design and synthesis.

  19. Nanostructured Amphiphilic Star-Hyperbranched Block Copolymers for Drug Delivery.

    PubMed

    Seleci, Muharrem; Seleci, Didem Ag; Ciftci, Mustafa; Demirkol, Dilek Odaci; Stahl, Frank; Timur, Suna; Scheper, Thomas; Yagci, Yusuf

    2015-04-21

    A robust drug delivery system based on nanosized amphiphilic star-hyperbranched block copolymer, namely, poly(methyl methacrylate-block-poly(hydroxylethyl methacrylate) (PMMA-b-PHEMA) is described. PMMA-b-PHEMA was prepared by sequential visible light induced self-condensing vinyl polymerization (SCVP) and conventional vinyl polymerization. All of the synthesis and characterization details of the conjugates are reported. To accomplish tumor cell targeting property, initially cell-targeting (arginylglycylaspactic acid; RGD) and penetrating peptides (Cys-TAT) were binding to each other via the well-known EDC/NHS chemistry. Then, the resulting peptide was further incorporated to the surface of the amphiphilic hyperbranched copolymer via a coupling reaction between the thiol (-SH) group of the peptide and the hydroxyl group of copolymer by using N-(p-maleinimidophenyl) isocyanate as a heterolinker. The drug release property and targeting effect of the anticancer drug (doxorobucin; DOX) loaded nanostructures to two different cell lines were evaluated in vitro. U87 and MCF-7 were chosen as integrin αvβ3 receptor positive and negative cells for the comparison of the targeting efficiency, respectively. The data showed that drug-loaded copolymers exhibited enhanced cell inhibition toward U87 cells in compared to MCF-7 cells because targeting increased the cytotoxicity of drug-loaded copolymers against integrin αvβ3 receptor expressing tumor cells. PMID:25816726

  20. Facile Synthesis and Characterization of Well-Defined Rod-Coil Block Copolymers Composed of Regioregular Poly(3-hexyl thiophene)

    NASA Astrophysics Data System (ADS)

    Moon, Hong Chul; Kim, Jin Kon

    2011-03-01

    We synthesized rod-coil block copolymers composed of regioregular poly(3-hexyl thiopene) (P3HT) block via anionic coupling reaction. Three different coil blocks (poly(2-vinyl pyridine) (P2VP) and polyisoprene (PI)) and poly(methyl methacrylate) (PMMA)) were selected. For the synthesis of P2VP- b -P3HT- b -P2VP and P2VP- b -P3HT- b -P2VP, the chain ends of the P3HT were capped by the aldehyde group. On the other hand, phenyl acrylate (PA)-capped P3HT was prepared for coupling reaction with living PMMA anions. When the excess amount of the used living anions was removed by column chromatography, all of the neat block copolymers showed lower PDI without leaving any homopolymers. We also investigated the optical property and thin film morphology of synthesized various block copolymers.

  1. Intriguing transmission electron microscopy images observed for perpendicularly oriented cylindrical microdomains of block copolymers

    NASA Astrophysics Data System (ADS)

    Ohnogi, Hiroshi; Isshiki, Toshiyuki; Sasaki, Sono; Sakurai, Shinichi

    2014-08-01

    Intriguing images of dislocation structures were observed by the transmission electron microscopy (TEM) technique for hexagonally packed cylindrical microdomains in a block copolymer (polystyrene-block-polyethylenebutylene-block-polystyrene triblock copolymer) film. The polystyrene (PS) cylinders were embedded in the polyethylenebutylene (PEB) matrix and oriented perpendicular to the surface of the thin section for the TEM observations. In order to understand such strange dislocation structures, we applied an image processing technique using two-dimensional Fourier transform (FT) and inverse Fourier transform (IFT) methods. It was found that these intriguing images were not ascribed to real dislocation structures but were fake ones due to the moiré effect caused by the overlapping of hexagons with a slightly mismatched orientation. Furthermore, grain boundaries in the ultrathin section can be identified by image processing using FT and IFT methods.Intriguing images of dislocation structures were observed by the transmission electron microscopy (TEM) technique for hexagonally packed cylindrical microdomains in a block copolymer (polystyrene-block-polyethylenebutylene-block-polystyrene triblock copolymer) film. The polystyrene (PS) cylinders were embedded in the polyethylenebutylene (PEB) matrix and oriented perpendicular to the surface of the thin section for the TEM observations. In order to understand such strange dislocation structures, we applied an image processing technique using two-dimensional Fourier transform (FT) and inverse Fourier transform (IFT) methods. It was found that these intriguing images were not ascribed to real dislocation structures but were fake ones due to the moiré effect caused by the overlapping of hexagons with a slightly mismatched orientation. Furthermore, grain boundaries in the ultrathin section can be identified by image processing using FT and IFT methods. Electronic supplementary information (ESI) available. See DOI: 10.1039/c

  2. Structure-Property Relationships in Polyolefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mansour, Ameara Salah

    Poly(cyclohexylethylene) (PCHE for a homopolymer or C in a block copolymer) is created by hydrogenating polystyrene, and this polymer exhibits interesting properties, such as a high glass transition temperature (147 °C), high flexural modulus (2.8 GPa), low stress optical coefficient (-0.2 * 10-9 Pa-1), and low cost. However, the inherently brittle nature of PCHE prevents it from being used in applications that simultaneously require high modulus, ductility, thermal stability, and optical clarity. Previous research has shown that incorporating PCHE into a block copolymer with rubbery poly(ethylene-alt-propylene) (P) or poly(ethylethylene) (EE) or semicrystalline polyethylene (E) results in a tough material. In some cases, applications also require specific mechanical or optical properties. In order to tune these properties, this research examined tuning crystallinity using two methods: (1) by controlling the microstructure of the soft block by synthesizing a random copolymer of E and EE, and (2) by blending high C content pentablock copolymers with semicrystalline and rubbery minority components. In the first study, diblock copolymers of C(EcoEE) also were used to understand how the microstructure of the random copolymer affects the thermodynamics of the system. In the second study, CECEC and CPCPC, designed to form the same morphology (hexagonally packed cylinders with glassy C matrices), and have similar order-to-disorder transition temperatures and domain spacings, were blended together. Isothermal crystallization experiments were used to determine how the confining E and P in one domain affects the crystallization process. The effect of architecture, the state of the minority component, and the percent crystallinity on the mechanical properties of high glass content materials was also examined. These results were compared to the mechanical properties of homopolymer PCHE, polystyrene, and polycarbonate. The processing conditions needed to create smooth films of

  3. Directed Self-assembly of Block Copolymer with Sub-15 nm Domain Spacing Using Nanoimprinted Photoresist Templates

    NASA Astrophysics Data System (ADS)

    Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Coughlin, E. Bryan; Xiao, Shuaigang; Russell, Thomas

    There has been increasing interest in preparing block copolymer thin films with ultra-small domain spacings for use as etching masks for ultra-high resolution nanolithography. One method to prepare block copolymer materials with small feature sizes is salt doping, increasing the Flory-Huggins interaction and allowing microphase separation to be maintained at lower molecular weights. Lamellae-forming P2VP- b-PS- b-P2VP block copolymer with various molecular weight was synthesized using RAFT polymerization with a dual functional chain transfer agent. Copper (II) Chloride or Gold (III) chloride was found to be selectively associated with P2VP block and increase the unfavorable interactions between PS and P2VP blocks, driving the disordered block copolymer into the ordered state. A 14 nm lamellar spacing of P2VP- b-PS- b-P2VP thin film was prepared using copper (II) Chloride doping after acetone vapor annealing on neutral brushes. Metallic nano-wire arrays were prepared after selective infiltration of platinum salt into the P2VP domain and oxygen plasma treatment. The directed self-assembly of salt doped P2VP- b-PS- b-P2VP triblock copolymer having long-rang lateral order on nanoimprinted photoresist templates with shallow trenches was also studied.

  4. Polythiophene-block-Polyfluorene and Polythiophene-block-Poly(fluorene-co-benzothiadiazole): insights into the self-assembly of all-conjugated block copolymers

    SciTech Connect

    Verduzco, Rafael; Botiz, Ioan; Dimasi, Elaine; Pickel, Deanna L; Hong, Kunlun; Kilbey, II, S Michael; Darling, Seth B.

    2011-01-01

    Block copolymers made by covalently linking two or more conjugated polymers have significant potential for organic optoelectronic applications, particularly those requiring a p/n junction. Herein, we report the structure of all-conjugated diblock copolymers poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene) and poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene-co-benzothiadiazole) in thin films and in the bulk. The diblock copolymers are prepared using a combination of Grignard metathesis polymerization and Suzuki polycondensation and purified using solvent extraction and column chromatography. 1H NMR, SEC, and UV/Visible absorbance measurements are used to characterize the materials and quantify the amount of homopolymer impurities. Thin films and bulk structure are characterized using a combination of differential scanning calorimetry, x-ray diffraction, small-angle x-ray scattering, and atomic force microscopy. Atomic force microscopy images reveal nanoscale lamellar domains in solvent-annealed diblock copolymer thin films, and peaks in x-ray diffraction data correspond to poly(3-hexylthiophene) crystallites. On cooling from temperatures above the crystallization temperature to below the crystallization temperature, two peaks appear in temperature-dependent small-angle x-ray scattering traces - one associated with poly(3-hexylthiophene) crystallites and a second low-angle peak indicative of a self-assembled nanostructured. These measurements show all-conjugated diblock copolymers self-assemble into nanoscale crystalline domains present throughout the bulk samples which may be useful for improving the performance of organic photovoltaics and organic light-emitting diodes.

  5. Block-copolymer-induced structure formation in microemulsions

    SciTech Connect

    Hilfiker, R.; Eicke, H.F.; Steeb, C.; Hofmeier, U. )

    1991-02-07

    Transient electric birefringence measurements were performed on water/AOT (sodium bis(2-ethylhexyl) sulfosuccinate)/isooctane microemulsions with various amounts of block-copoly(oxyethylene/isoprene/oxyethylene) added. The authors could show that addition of the copolymer leads to a formation of nanodroplet (ND)-copolymer-aggregates. The contributions of NDs and aggregates to the induced birefringence could easily be separated because the NDs exhibited a negative and the aggregates a positive induced birefringence and because the time scales corresponding to the two processes were different.

  6. Beyond Spherical Micelles in Styrene-Isoprene Block Copolymer Solutions

    NASA Astrophysics Data System (ADS)

    Bang, Joona; Lodge, Timothy P.

    2004-03-01

    As macromolecular surfactants, block copolymers have been shown to self-assemble into various microstructures. Many studies have focused on aqueous systems, in which the strongly amphiphilic characteristics of the polymers lead to various micellar shapes (worms, vesicles, compound micelles, etc). However, such micellar shape changes are apparently very rare in organic systems. We report systematic shape changes of the micelles in styrene-isoprene block copolymer solutions. Remarkably, such changes could be accomplished in a single block copolymer by varying the solvent selectivity. We studied two asymmetric poly(styrene-b-isoprene) diblock copolymers with the styrene volume fractions of approximately 0.15 in a series of solvents with varying styrene selectivity, dibuthyl phthalate, diethyl phthalate, and dimethyl phthalate. The degree of the solvent selectivity was adjusted by mixing two solvents. With increasing solvent selectivity, the micellar shape changes from cylindrical micelles to bilayer vesicles, and then phase-separates, reflecting the changing interfacial curvature induced by solvent selectivity. The detailed micellar morphologies were characterized by dynamic light scattering, rheology, electron microscopy, and small angle x-ray scattering.

  7. Formation and Characterization of Anisotropic Block Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

    2012-02-01

    Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

  8. Gas Permeation through Polystyrene-Poly(ethylene oxide) Block Copolymers

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel, Jr.; Minelli, Matteo; Giacinti-Baschetti, Marco; Balsara, Nitash

    2013-03-01

    Lithium air batteries are a potential technology for affordable energy storage. They consist of a lithium metal anode and a porous air cathode separated by a solid polymer electrolyte membrane, such as PEO/LiTFSI (PEO = poly(ethylene oxide), LiTFSI = lithium bis-trifluoromethane sulfonimide). For extended operation of such a battery, the polymer electrolyte must conduct lithium ions while blocking electrons and gases present in air. In order to maintain a pressure difference the membrane must be mechanically robust, which can be achieved by incorporating the PEO into a block copolymer with a glassy block such as PS (PS = polystyrene). To protect the lithium electrode, the membrane must have low permeability to gases in air such as CO2, N2, and O2. We have therefore studied the permeation of pure gases through a PS-PEO block copolymer. A high molecular weight, symmetric block copolymer with a lamellar morphology was used to cast free-standing membranes. Gas permeability was measured through these membranes with a standard, pressure-based technique. A model was developed to account for transport through the polymer membrane consisting of semi-crystalline PEO lamellae and amorphous PS lamellae. PEO crystallinity was extracted from the permeation model and compares well with values from differential scanning calorimetry measurements.

  9. Grain Rotation in Ion-Complexed Symmetric Diblock Copolymer Thin Films under an Electric Field

    SciTech Connect

    Wang,J.; Leiston-Belanger, J.; Sievert, J.; Russell, T.

    2006-01-01

    In symmetric polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer thin films, lithium-PMMA complexes were formed with the addition of lithium chloride (LiCl), significantly increasing both {chi} and dielectric constant. These led to a transition in the kinetic pathway of the orientation of lamellar microdomains under an applied electric field from a disruption and re-formation of the microdomains to a grain rotation mediated by movement of defects. By controlling the number of lithium-PMMA complexes, the microdomain alignment is possibly regulated in PS-b-PMMA copolymer thin films.

  10. Synthesis and interactions with blood of polyetherurethaneurea/polypeptide block copolymers.

    PubMed

    Ito, Y; Miyashita, K; Kashiwagi, T; Imanishi, Y

    1993-01-01

    Polyurethane/polypeptide block copolymers were synthesized. Infrared spectroscopy and differential scanning calorimetry revealed that in the block copolymers both segments undergo phase-mixing, while in polyurethane/polypeptide blend both components undergo phase-separation. Contact angle measurement showed that in the block copolymers polyurethane segments tended to appear on the membrane surface, whereas in polyurethane/polypeptide blend polypeptide components appeared on the membrane surface. In vitro nonthrombogenicity of the block copolymers was similar to that of homopolymers or polymer blends, though adhesion and deformation of platelets were suppressed on the block copolymer membranes. PMID:8260582

  11. Self-Assembly of Rod-Coil Block Copolymers And Their Application in Electroluminescent Devices

    SciTech Connect

    Tao, Y.; Ma, B.; Segalman, R.A.

    2009-05-26

    The formation of alternating electron transporting and hole transporting 15 nm lamellae within the active layer of an organic light-emitting diode (OLED) is demonstrated to improve device performance. A new multifunctional bipolar rod-coil block copolymer containing a poly(alkoxy phenylenevinylene) (PPV) rod-shaped block as the hole transporting and emitting material and a poly(vinyloxadiazole) coil-shaped electron transporting block is synthesized. This new block copolymer is the active material of a self-assembling multicomponent electroluminescent device that can be deposited in a single step. In the thin film, grazing incidence X-ray scattering and transmission electron microscopy demonstrate that the layers form grains which are oriented bimodally: parallel and perpendicular from the anode. In this mixed orientation, the device demonstrates better performance than those with either pure PPV or a blend of the two analogous homopolymers as the active materials, i.e., higher external quantum efficiency (EQE) and brightness. This improved device performance is mainly attributed to the bipolar functionality and microphase separation of the block copolymer, which provide highly efficient hole and electron recombination at the nanodomain interfaces.

  12. Self-Assembly of Rod-Coil Block Copolymers and Their Application in Electroluminescent Devices

    SciTech Connect

    Tao, Yuefei; Ma, Biwu; Segalman, Rachel A.

    2008-11-18

    The formation of alternating electron transporting and hole transporting 15 nm lamellae within the active layer of an organic light-emitting diode (OLED) is demonstrated to improve device performance. A new multifunctional bipolar rod-coil block copolymer containing a poly(alkoxy phenylenevinylene) (PPV) rod-shaped block as the hole transporting and emitting material and a poly(vinyloxadiazole) coil-shaped electron transporting block is synthesized. This new block copolymer is the active material of a self-assembling multicomponent electroluminescent device that can be deposited in a single step. In the thin film, grazing incidence X-ray scattering and transmission electron microscopy demonstrate that the layers form grains which are oriented bimodally: parallel and perpendicular from the anode. In this mixed orientation, the device demonstrates better performance than those with either pure PPV or a blend of the two analogous homopolymers as the active materials, i.e., higher external quantum efficiency (EQE) and brightness. This improved device performance is mainly attributed to the bipolar functionality and microphase separation of the block copolymer, which provide highly efficient hole and electron recombination at the nanodomain interfaces.

  13. Percolating transport and the conductive scaling relationship in lamellar block copolymers under confinement.

    PubMed

    Diederichsen, Kyle M; Brow, Ryan R; Stoykovich, Mark P

    2015-03-24

    The topology and transport behavior of the lamellar morphology self-assembled by block copolymers in thin films are shown to depend on the length scale over which they are characterized and can be described by percolation in a network under confinement. Gold nanowires replicating the lamellar morphology were fabricated via self-assembled poly(styrene-block-methyl methacrylate) thin films and a lift-off pattern transfer process. The lamellar morphology exhibits long-range connectivity (macroscopic scale); however, characterization of electrical conduction over confined areas (5-500 μm) demonstrates a discrete probability of disconnection that arises due to the underlying network structure and a lack of self-similarity at these microscale dimensions. In particular, it is proved that the lamellar network morphology under confinement has a conductance that is nonlinear with channel length or width. The experimental results are discussed in terms of percolation theory, and a simple, two-dimensional Monte Carlo model is shown to predict the key trends in the network topology and conductance in lamellar block copolymers, including the dependencies on composition, extent of spatial confinement, and confinement geometry. These results highlight the need to exquisitely control or engineer the self-assembled nanostructured pathways formed by block copolymers to ensure consistent device performance for any application that depends upon percolating material, ionic, or electrical transport, especially when confined in any dimension. It is also concluded that the two most promising approaches for enhancing conductivity in block copolymer materials may be achieved either at the limits of (1) perfectly oriented, single-crystalline or (2) high defect density, polycrystalline microphase separated morphologies and that nanostructured systems with intermediate defect densities would be detrimental to transport in confined systems. PMID:25756653

  14. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane-polyacrylate block copolymers

    NASA Astrophysics Data System (ADS)

    Li, Xiaohui; Zhao, Yunhui; Li, Hui; Yuan, Xiaoyan

    2014-10-01

    Five polymethyltrifluoropropylsiloxane (PMTFPS)-polyacrylate block copolymers (PMTFPS-b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10-50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at -15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS-b-polyacrylate copolymer can be used as icephobic coating materials potentially.

  15. Influence of Chirality in Ordered Block Copolymer Phases

    NASA Astrophysics Data System (ADS)

    Prasad, Ishan; Grason, Gregory

    2015-03-01

    Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

  16. Periodic nanostructures from self assembled wedge-type block-copolymers

    SciTech Connect

    Xia, Yan; Sveinbjornsson, Benjamin R.; Grubbs, Robert H.; Weitekamp, Raymond; Miyake, Garret M.; Piunova, Victoria; Daeffler, Christopher Scot

    2015-06-02

    The invention provides a class of wedge-type block copolymers having a plurality of chemically different blocks, at least a portion of which incorporates a wedge group-containing block providing useful properties. For example, use of one or more wedge group-containing blocks in some block copolymers of the invention significantly inhibits chain entanglement and, thus, the present block copolymers materials provide a class of polymer materials capable of efficient molecular self-assembly to generate a range of structures, such as periodic nanostructures and microstructures. Materials of the present invention include copolymers having one or more wedge group-containing blocks, and optionally for some applications copolymers also incorporating one or more polymer side group-containing blocks. The present invention also provides useful methods of making and using wedge-type block copolymers.

  17. A Simple Route to Highly Oriented and Ordered Nanoporous Block Copolymer Templates

    SciTech Connect

    Park,S.; Wang, J.; Kim, B.; Xu, J.; Russell, T.

    2008-01-01

    Controlling the orientation and lateral ordering of the block copolymer microdomains is essential to their use as templates and scaffolds for the fabrication of nanostructured materials. In addition, a process must be robust, simple to implement, and rapid, and should not introduce disruptive processing steps that would impede their use. Here, we describe thin films of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymers, spin-coated from mixed solvents that show highly oriented, cylindrical microdomains with a high degree of order on a wide range of substrates, including silicon oxide, polystyrene, germanium, polyimide, and poly(butylene terephthalate). In addition, the preferential solvation of the P4VP block with an alcohol caused a surface reconstruction that resulted in the formation of a nanoporous film upon drying. The evaporation of gold onto the reconstructed films produced thermally stable and reactive ion etching resistant films.

  18. DNA block copolymers: functional materials for nanoscience and biomedicine.

    PubMed

    Schnitzler, Tobias; Herrmann, Andreas

    2012-09-18

    We live in a world full of synthetic materials, and the development of new technologies builds on the design and synthesis of new chemical structures, such as polymers. Synthetic macromolecules have changed the world and currently play a major role in all aspects of daily life. Due to their tailorable properties, these materials have fueled the invention of new techniques and goods, from the yogurt cup to the car seat belts. To fulfill the requirements of modern life, polymers and their composites have become increasingly complex. One strategy for altering polymer properties is to combine different polymer segments within one polymer, known as block copolymers. The microphase separation of the individual polymer components and the resulting formation of well defined nanosized domains provide a broad range of new materials with various properties. Block copolymers facilitated the development of innovative concepts in the fields of drug delivery, nanomedicine, organic electronics, and nanoscience. Block copolymers consist exclusively of organic polymers, but researchers are increasingly interested in materials that combine synthetic materials and biomacromolecules. Although many researchers have explored the combination of proteins with organic polymers, far fewer investigations have explored nucleic acid/polymer hybrids, known as DNA block copolymers (DBCs). DNA as a polymer block provides several advantages over other biopolymers. The availability of automated synthesis offers DNA segments with nucleotide precision, which facilitates the fabrication of hybrid materials with monodisperse biopolymer blocks. The directed functionalization of modified single-stranded DNA by Watson-Crick base-pairing is another key feature of DNA block copolymers. Furthermore, the appropriate selection of DNA sequence and organic polymer gives control over the material properties and their self-assembly into supramolecular structures. The introduction of a hydrophobic polymer into DBCs

  19. Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy

    NASA Astrophysics Data System (ADS)

    Rokhlenko, Yekaterina; Gopinadhan, Manesh; Osuji, Chinedum O.; Zhang, Kai; O'Hern, Corey S.; Larson, Steven R.; Gopalan, Padma; Majewski, Paweł W.; Yager, Kevin G.

    2015-12-01

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δ χ , that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δ χ ≈2 ×1 0-8. From field-dependent scattering data, we estimate that grains of ≈1.2 μ m are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

  20. Confinement of elastomeric block copolymers via forced assembly coextrusion.

    PubMed

    Burt, Tiffani M; Keum, Jong; Hiltner, Anne; Baer, Eric; Korley, Lashanda T J

    2011-12-01

    Forced assembly processing provides a unique opportunity to examine the effects of confinement on block copolymers (BCPs) via conventional melt processing techniques. The microlayering process was utilized to produce novel materials with enhanced mechanical properties through selective manipulation of layer thickness. Multilayer films consisting of an elastomeric, symmetric block copolymer confined between rigid polystyrene (PS) layers were produced with layer thicknesses ranging from 100 to 600 nm. Deformation studies of the confined BCP showed an increase in ductility as the layer thickness decreased to 190 nm due to a shift in the mode of deformation from crazing to shear yielding. Postextrusion annealing was performed on the multilayer films to investigate the impact of a highly ordered morphology on the mechanical properties. The annealed multilayer films exhibited increased toughness with decreasing layer thickness and resulted in homogeneous deformation compared to the as-extruded films. Multilayer coextrusion proved to be an advantageous method for producing continuous films with tunable mechanical response. PMID:22124208

  1. Magnetic alignment of block copolymer microdomains by intrinsic chain anisotropy

    DOE PAGESBeta

    Rokhlenko, Yekaterina; Yager, Kevin G.; Gopinadhan, Manesh; Osuji, Chinedum O.; Zhang, Kai; O'Hern, Corey S.; Larson, Steven R.; Gopalan, Padma; Majewski, Pawel W.

    2015-12-18

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ ≈ 2×10–8. From field-dependent scattering data, we estimate that grains of ≈ 1.2 μm are present during alignment. Furthermore, these results demonstrate that intrinsic anisotropymore » is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.« less

  2. Magnetic alignment of block copolymer microdomains by intrinsic chain anisotropy

    SciTech Connect

    Rokhlenko, Yekaterina; Yager, Kevin G.; Gopinadhan, Manesh; Osuji, Chinedum O.; Zhang, Kai; O'Hern, Corey S.; Larson, Steven R.; Gopalan, Padma; Majewski, Pawel W.

    2015-12-18

    We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ ≈ 2×10–8. From field-dependent scattering data, we estimate that grains of ≈ 1.2 μm are present during alignment. Furthermore, these results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

  3. Development and integration of systems with enhanced resolutions based on Si-containing block copolymers for line space applications

    NASA Astrophysics Data System (ADS)

    Fleury, G.; Aissou, K.; Mumtaz, M.; Chevalier, X.; Nicolet, C.; Navarro, C.; Fernandez-Regulez, M.; Pimenta-Barros, P.; Tiron, R.; Brochon, C.; Cloutet, E.; Hadziioannou, G.

    2015-03-01

    While directed self-assembly based on poly(styrene)-block-poly(methylmethacrylate) block copolymers (BCP) for contact shrink or multiplication applications approaches industrial maturity, new systems with the ability to self-assemble with sub-20 nm features need to be evaluated taking into account the integration requirements (in terms of solvent, thermal budget, etching capability,…). In this contribution, two different systems Si-containing BCP systems will be presented targeting line/space applications. These two systems are characterized by a high segregation strength allowing the design of block copolymers with sub-20 nm period while high etching contrast inherent to the Si-containing block could be achieved between the different blocks. Firstly original poly(dimethylsilacyclobutane)-blockpoly( methylmethacrylate) (PDMSB-b-PMMA) block copolymers showing hexagonal arrays of PDMBS cylinders have been developed. Study of the PDMSB-b-PMMA self-assembly both on free surface and on patterned substrates show its high potential since long range order arrays can be obtained by a rapid thermal annealing treatment. Besides preliminary results on their track integration is discussed with a demonstration of density multiplication up to 18. The second system consists of poly(dimethylsiloxane)-block-poly(lactid acid) block chains which self-assemble into PDMS cylinders in thin film configuration. Such block copolymer system provides an easy access to line/space arrays of parallel PDMS cylinders which can be subsequently transferred into the desired stack layers through plasma etching.

  4. SEPARATION OF VOLATILE ORGANIC COMPOUNDS FROM AQUEOUS SOLUTIONS BY PERVAPORATION USING S-B-S BLOCK COPOLYMER MEMBRANES.

    EPA Science Inventory

    Composite membranes of a block copolymer of styrene and butadiene (S-B-S) were cast on highly porous, hydrophobic thin films of PTFE, and used for the separation and recovery of volatile organic compounds (VOCs) from aqueous solutions by pervaporation. Trichloroethane, trichloroe...

  5. SEPARATION OF VOLATILE ORGANIC COMPOUNDS FROM AQUEOUS SOLUTIONS BY PERVAPORATION USING S-B-S BLOCK COPOLYMER MEMBRANES

    EPA Science Inventory

    Composite membranes of a block copolymer of styrene and butadiene (S-B-S) were cast on highly porous, hydrophobic thin films of PTFE and used for the separation and recovery of volatile organic compounds (VOCs) from aqueous solutions by pervaporation. Trichloroethane, trichloroe...

  6. Electrically Tunable Soft-Solid Block Copolymer Structural Color.

    PubMed

    Park, Tae Joon; Hwang, Sun Kak; Park, Sungmin; Cho, Sung Hwan; Park, Tae Hyun; Jeong, Beomjin; Kang, Han Sol; Ryu, Du Yeol; Huh, June; Thomas, Edwin L; Park, Cheolmin

    2015-12-22

    One-dimensional photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid (IL) swollen block copolymer (BCP) films. Placement of a polymer/ionic liquid film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2-vinylpyridine) (PS-b-QP2VP) copolymer SC film allowed the development of red (R), green (G), and blue (B) full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3 to +6 V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device. PMID:26505787

  7. Solubilization of a homopolymer in a block copolymer

    SciTech Connect

    Jeon, K.J.; Roe, R.J. . Dept of Materials Science and Engineering)

    1994-04-25

    Blends containing styrene-butadiene diblock copolymer (50 wt % styrene content) and polystyrene of various molecular weights are studied by light scattering, transmission electron microscopy, and small-angle X-ray scattering. The solubility of polystyrene in the styrene domain of the block copolymer is governed by the ratio of the homopolymer molecular weight to the block molecular weight. A finite solubility limit exists when this ratio exceeds [approximately]1. The lamellar repeat period increases linearly as more polystyrene is added, but the butadiene layer thickness remains constant, signifying that the average interfacial area occupied by a copolymer junction point does not change with added polystyrene. This contrasts to the case found by the others that the average area per junction point increases when the added homopolymer is smaller than the block size. Small-angle X-ray scattering patterns obtained from samples having lamellar morphology are described by an idealized model in which layers of styrene and butadiene of randomly varying thicknesses with a diffuse interface between them are stacked parallel.

  8. Proton Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan; Tyagi, Madhu; Reimer, Jeffrey; Segalman, Rachel

    2011-03-01

    Nanostructured block copolymer/ionic liquid mixtures are of interest for creating membranes having high proton conductivity coupled with high thermal stability. In these mixtures, it is anticipated that nanoconfinement to block copolymer domains will affect ionic liquid proton transport properties. Using pulsed-field gradient NMR and quasi-elastic neutron scattering, this relationship has been investigated for mixtures of poly(styrene-b- 2-vinylpyridine) (S2VP) with ionic liquids composed of imidazole and bis(trifluoromethane)sulfonimide (HTFSI), where the ionic liquids selectively reside in the P2VP domains of the block copolymer. Proton mobility is highest in the neat ionic liquids when there is an excess of imidazole compared to HTFSI due to proton hopping between hydrogen-bonded imidazoles. As predicted, the amount of proton hopping can be tuned by nanoconfinement, as evidenced by the finding that a lamellar mixture of an imidazole- excess ionic liquid with S2VP has greater proton mobility than a corresponding disordered mixture of the ionic liquid with P2VP homopolymer.

  9. Redox-controlled micellization of organometallic block copolymers.

    PubMed

    Rider, David A; Winnik, Mitchell A; Manners, Ian

    2007-11-21

    Polystyrene-block-polyferrocenylsilane (PS-b-PFS) diblock copolymers were stoichiometrically oxidized in solution using salts of the one-electron oxidant tris(4-bromophenyl)ammoniumyl. Due to a redox-induced polarity change for the PFS block, self-assembly into well-defined spherical micelles occurs. The micelles are composed of a core of partially oxidized PFS segments and a corona of PS. When the micellar solutions were treated with the reducing agent decamethylcobaltocene, the spherical micelles disassemble and regenerate unassociated and pristine PS-b-PFS free chains. PMID:17971963

  10. Transmission electron microscopy of polymer blends and block copolymers

    NASA Astrophysics Data System (ADS)

    Gomez, Enrique Daniel

    Transmission electron microscopy (TEM) of soft matter is a field that warrants further investigation. Developments in sample preparation, imaging and spectroscopic techniques could lead to novel experiments that may further our understanding of the structure and the role structure plays in the functionality of various organic materials. Unlike most hard materials, TEM of organic molecules is limited by the amount of radiation damage the material can withstand without changing its structure. Despite this limitation, TEM has been and will be a powerful tool to study polymeric materials and other soft matter. In this dissertation, an introduction of TEM for polymer scientists is presented. The fundamentals of interactions of electrons with matter are described using the Schrodinger wave equation and scattering cross-sections to fully encompass coherent and incoherent scattering. The intensity, which is the product of the wave function and its complex conjugate, shows no perceptible change due to the sample. Instead, contrast is generated through the optical system of the microscope by removing scattered electrons or by generating interference due to material-induced phase changes. Perhaps the most challenging aspect of taking TEM images, however, is sample preparation, because TEM experiments require materials with approximately 50 nm thickness. Although ultramicrotomy is a well-established powerful tool for preparing biological and polymeric sections for TEM, the development of cryogenic Focused Ion Beam may enable unprecedented cross-sectional TEM studies of polymer thin films on arbitrary substrates with nanometer precision. Two examples of TEM experiments of polymeric materials are presented. The first involves quantifying the composition profile across a lamellar phase obtained in a multicomponent blend of saturated poly(butadiene) and poly(isobutylene), stabilized by a saturated poly(butadiene) copolymer serving as a surfactant, using TEM and self

  11. Flow Controlled Solvent Vapor Annealing of Block Copolymers for Lithographic Applications

    NASA Astrophysics Data System (ADS)

    Gotrik, Kevin Willy

    Self-assembly of block copolymer thin-films may provide an inexpensive alternative to patterning lithographic features below the resolution limits of traditional optical methods. Block copolymers (BCPs) are polymers made of two or more distinct monomer /block units that are covalently bonded. Due to their differences in surface energy, the different blocks tend to phase segregate like oil and water; but because of the covalent linkage, this segregation is practically limited to size scales ranging from only a few nm to ≈ 100 nm. A thin film of a BCP can be used in much the same way as a photoresist in the lithographic process, whereas a desired pattern morphology can be obtained by etching one block away and leaving behind a self-assembled hard mask for the underlying substrate. After a thin film of BCP is coated onto a given substrate, the BCP must be given an annealing step, where the disordered entangled polymer networks can be allowed to diffuse and equilibrate into lower free energy configurations which result in periodic patterns of micelles with different morphologies such as spheres, in/out of plane cylinders, etc. This work explored the technique of solvent vapor annealing, where organic solvents were allowed to interact with BCP thin films to facilitate annealing and act as surrogates for the different BCP polymer blocks. This allowed for a wide range of control over the BCP self-assembly (morphology, periodicity, etc.) for a given molecular weight BCP. Additionally, by adding heat at critical times during the self-assembly, time scales for solvent vapor enhanced self-assembly could be reduced from hours to seconds making the prospects for this technology to become industrially applicable more promising. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

  12. Block copolymers for alkaline fuel cell membrane materials

    NASA Astrophysics Data System (ADS)

    Li, Yifan

    Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC

  13. Contrast enhanced diffusion NMR: quantifying impurities in block copolymers for DSA

    NASA Astrophysics Data System (ADS)

    Wojtecki, Rudy; Porath, Ellie; Vora, Ankit; Nelson, Alshakim; Sanders, Daniel

    2016-03-01

    Block-copolymers (BCPs) offer the potential to meet the demands of next generation lithographic materials as they can self-assemble into scalable and tailorable nanometer scale patterns. In order for these materials to find wide spread adoption many challenges remain, including reproducible thin film morphology, for which the purity of block copolymers is critical. One of the sources of impurities are reaction conditions used to synthesize block copolymers that may result in the formation of homopolymer as a side product, which can impact the quality and the morphology of self-assembled features. Detection and characterization of these homopolymer impurities can be challenging by traditional methods of polymer characterization. We will discuss an alternate NMR-based method for the detection of homopolymer impurities in block copolymers - contrast enhanced diffusion ordered spectroscopy (CEDOSY). This experimental technique measures the diffusion coefficient of polymeric materials in the solution allowing for the `virtual' or spectroscopic separation of BCPs that contain homopolymer impurities. Furthermore, the contrast between the diffusion coefficient of mixtures containing BCPs and homopolymer impurities can be enhanced by taking advantage of the chemical mismatch of the two blocks to effectively increase the size of the BCP (and diffusion coefficient) through the formation of micelles using a cosolvent, while the size and diffusion coefficient of homopolymer impurities remain unchanged. This enables the spectroscopic separation of even small amounts of homopolymer impurities that are similar in size to BCPs. Herein, we present the results using the CEDOSY technique with both first generation BCP system, poly(styrene)-b-poly(methyl methacrylate), as well as a second generation high-χ system.

  14. Biodegradable PELA block copolymers: in vitro degradation and tissue reaction.

    PubMed

    Younes, H; Nataf, P R; Cohn, D; Appelbaum, Y J; Pizov, G; Uretzky, G

    1988-01-01

    Degradation of, and tissue reaction elicited by a series of polyethylene oxide (PEO)/polylactic acid (PLA) PELA block copolymers were studied in vitro and in vivo. In particular, the effect of pH, temperature and enzymatic activity was addressed. The mass loss was faster, the more basic the media, while, expectedly, PELA copolymers degraded faster with the higher temperature. The addition of an enzyme (carboxylic ester hydrolase) had no effect. The degradation process strongly affected the mechanical properties of the materials under investigation, the elongation at break dropping drastically after two days of degradation. After seven days, only gross observation of the extensively degraded samples was possible. The in vivo studies compared the tissue reaction elicited by various PELA copolymers to that evoked by PLA. Evaluation of tissue reaction observed with a PELA sample after sterilization with gamma radiation showed acute inflammation with considerable dispersion of the material, 12 days after implantation. The granulomatous reaction observed with PELA copolymers after ethylene oxide sterilization was identical to the reaction observed with PLA. PMID:3064826

  15. Biomembrane mimics made from block copolymers

    NASA Astrophysics Data System (ADS)

    Discher, Bohdana; Won, You-Yeon; Lee, James; Bermudez, Harry; Bates, Frank

    2000-03-01

    Synthetic, `super'-amphiphilic polymers have been used to self assemble cell-sized vesicles having some unique properties. Membrane elasticity measures together with cryo-TEM analyses prove consistent with a hyper-thick structure in comparison to lipid membranes. The increased thickness also explains the enhanced toughness of the polymer membranes as well as their reduced permeability. The results raise fundamental questions as to the reasons for nature's `thin' designs and, together with simple measures of biocompatibility, suggest obvious applications. In addition, the reduced viscosity and high reactivity achievable in these membranes enables covalent cross-linking which, at a qualitative level, replicates the shear resilience of polymerized structures like the spectrin network of the red cell. Extensive cross-linking over many microns is demonstrated through observable transfer into chloroform or air without detectable loss of either surface or contents. Although, shear-based estimates of crosslink densities substantiate the picture that these membranes are more hard than soft, dilution of the crosslinkable polymers leads to 'brittle' membranes that may provide new opportunites for tuned release.

  16. Combinatorial Block Copolymer Ordering on Tunable Rough Substrates

    SciTech Connect

    Kulkarni, Manish M.; Yager, Kevin G.; Sharma, Ashutosh; Karim, Alamgir

    2012-10-25

    Morphology control of block copolymer (BCP) thin films through substrate interaction via controlled roughness parameters is of significant interest for numerous high-tech applications ranging from solar cells to high-density storage media. While effects of substrate surface energy (SE) and roughness (R) on BCP morphology have been individually investigated, their synergistic effects have not been explored in any systematic manner. Interestingly, orientation response of BCP to changes in SE can be similar to what can be accomplished with variations in R. Here we present a novel approach for orienting lamellar BCP films of poly(styrene)-block-poly(methyl methacrylate) (PS-PMMA) on spin-coated xerogel (a dried gel of silica nanoparticle network) substrate with simultaneously tunable surface energy, {gamma}{sub s} {approx} 29-53 mJ/m{sup 2}, by UVO exposure and roughness, R{sub rms} {approx} 0.5-30 nm, by sol-gel processing steps of regulating the catalyst concentration and sol aging time. As in previous BCP orientation studies on 20 nm diameter monodisperse silica nanoparticle coated surface, we find a similar but broadened oscillatory BCP orientation behavior with film thickness due to the random rather than periodic rough surfaces. We also find that higher random roughness amplitude is not the necessary criteria for obtaining a vertical orientation of BCP lamellae. Rather, a high surface fractal dimension (D{sub f} > 2.4) of the rough substrate in conjunction with an optimal substrate surface energy {gamma}{sub s} {approx} 29 mJ/m{sup 2} results in 100% vertically oriented lamellar microdomains. The AFM measured film surface microstructure correlates well with the internal 3D BCP film structure probed by grazing incidence small-angle X-ray scattering (GISAXS) and rotational small-angle neutron scattering (SANS). In contrast to tunable self-assembled monolayer (SAM)-coated substrates, the xerogel films are very durable and retain their chemical properties over period

  17. Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

    PubMed Central

    2016-01-01

    Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this paper, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (ϕNpm) values ranging from 0.13 to 0.44 and dispersity (Đ) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with ϕNpm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. We demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers. PMID:27134312

  18. Modeling line-edge roughness in lamellar block copolymer systems

    NASA Astrophysics Data System (ADS)

    Patrone, Paul N.; Gallatin, Gregg M.

    2012-03-01

    Block copolymers oer an appealing alternative to current lithographic techniques with regard to fabrication of the next generation micro-processors. However, if copolymers are to be useful on an industrial manufacturing scale, they must meet or exceed lithography specications for placement and line edge roughness (LER) of resist features. Here we discuss a eld theoretic approach to modeling the LER of lamellar microdomain interfaces in a strongly segregated block copolymer system; specically, we derive a formula for the LER as a functions of the Flory Huggins parameter and the index of polymerization N. Our model is based on the Leibler-Ohta-Kawasaki energy functional. We consider a system with a nite number of phase separated microdomains and also show how the LER depends on distance of the microdomain interface from the system boundary. Our results suggest that in order to meet target LER goals at the 15 nm, 11 nm, and 6 nm nodes, must be increased by a factor of at least 5 above currently attainable values.

  19. Spatial position control of nanofeatures assisted by nanoporous templates fabricated by block copolymer based lithography

    NASA Astrophysics Data System (ADS)

    Lee, Dong Hyun; Lee, Dong-Eun

    2015-03-01

    Herein, we demonstrated a unique method to control spatial arrangement of nanostructures by using topographically patterned substrates. The thin films of block copolymers (BCPs) were firstly prepared on a thin layer of poly(vinyl alcohol) (PVA). Then to induce ordering of the BCPs, the thin films were solvent-annealed in organic solvent vapors. The BCP thin films were then utilized as a mask to fabricate ordered PVA nanopores by reactive ion etching. Different types of BCP micelles were sequentially spin-coated on the nanoporous PVA film. Interestingly, the BCP micelles having hydrophobic surface could immediately be self-assembled due to synergetic effects of surface energy difference and height contrast of the PVA film during evaporation of a suspension solvent. In addition, by combining topographically patterned substrates, long-rage lateral ordering of BCP micelles depending on inter-distance and diameter of the PVA nanopores were effectively achieved over whole surface area.

  20. Long-Range Ordering of Block Copolymers on Well-Controlled Patterned Substrates

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Eun; Kim, Nam-Kyun; Park, Jina; Lee, Donghyun

    2015-03-01

    In this study, we achieved long-range ordering of block copolymers (BCPs) by combining solvent-annealing process and well-controlled patterned substrates. Nano-lines of poly(tetrafluoro ethylene) (PTFE) were firstly fabricated in large area as a PTFE bar was rubbed on Si substrates at 340 °C. The amplitude and pitch distance of PTFE nanolines were around 17 nm and 150 nm, respectively. Then, asymmetric polystyrene-block-poly(2-vinylpyridine) copolymers (PS- b-P2VP) were subsequently spin-coated on the patterned substrates after a thin layer of poly(vinyl alcohol) (PVA) was prepared on the PTFE patterned substrates to enhance the wettability of BCP thin films. As BCP thin films were solvent-annealed in vapor of organic solvents, highly ordered BCP nanostructures oriented either parallel or perpendicular to the surface were generated in large area. In addition, the nanopatterns were successfully transferred to the underlying PVA layer or Si substrate by dry etching. Thus, the resulting nanopatterns were utilized as templates to synthesize inorganic nanofeatures. The ordering behavior of BCP thin films on the patterned substrates was characterized by using AFM, SEM and GI-SAXS.

  1. Metal Nanoparticle/Block Copolymer Composite Assembly and Disassembly.

    PubMed

    Li, Zihui; Sai, Hiroaki; Warren, Scott C; Kamperman, Marleen; Arora, Hitesh; Gruner, Sol M; Wiesner, Ulrich

    2009-01-01

    Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organic-inorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,N-di-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules. PMID:21103025

  2. Organization of nanoparticles on hard substrates using block copolymer films as templates.

    PubMed

    Minelli, Caterina; Geissbuehler, Isabelle; Hinderling, Christian; Heinzelmann, Harry; Vogel, Horst; Pugin, Raphael; Liley, Martha

    2006-06-01

    We present a technique for the organization of pre-synthesized nanoparticles on hard substrates, using block copolymer films as sacrificial templates. A thin block copolymer film is dip-coated on the substrate of interest and the sample is exposed to a solution containing nanoparticles. Spontaneous preferential adsorption of the nanoparticles on one phase of the block copolymer film results in their lateral organization. An oxygen plasma etch is used to remove the polymer film; the nanoparticles end up organized on the substrate. We demonstrate that this is a general approach for the patterning of inorganic nanoparticles on hard substrates, showing the organization of metal and semiconductor nanoparticles having different chemistries at the particle/solvent and solvent/polymer interfaces. The nanoparticle patterns that we present have typical periodicities in the nanometer scale. In some cases, microcontact printing is used to create a double length scale of organization, on the micrometer and on the nanometer level. The characteristic periodicity of the template is studied with respect to the nanoparticle size in order to optimize the organization. Finally, we describe how to extend this technique for the production of continuous gold nanowires on hard substrates. We expect that the flexibility of this approach and the degree of control that can be obtained over nanoparticle organization should make it a powerful tool for nanoscale fabrication. PMID:17025059

  3. Sequential Block Copolymer Self-Assemblies Controlled by Metal-Ligand Stoichiometry.

    PubMed

    Yin, Liyuan; Wu, Hongwei; Zhu, Mingjie; Zou, Qi; Yan, Qiang; Zhu, Liangliang

    2016-06-28

    While numerous efforts have been devoted to developing easy-to-use probes based on block copolymers for detecting analytes due to their advantages in the fields of self-assembly and sensing, a progressive response on block copolymers in response to a continuing chemical event is not readily achievable. Herein, we report the self-assembly of a 4-piperazinyl-1,8-naphthalimide based functional block copolymer (PS-b-PN), whose self-assembly and photophysics can be controlled by the stoichiometry-dependent metal-ligand interaction upon the side chain. The work takes advantages of (1) stoichiometry-controlled coordination-structural transformation of the piperazinyl moiety on PS-b-PN toward Fe(3+) ions, thereby resulting in a shrinkage-expansion conversion of the self-assembled nanostructures in solution as well as in thin film, and (2) stoichiometry-controlled competition between photoinduced electron transfer and spin-orbital coupling process upon naphthalimide fluorophore leading to a boost-decline emission change of the system. Except Fe(3+) ions, such a stoichiometry-dependent returnable property cannot be observed in the presence of other transition ions. The strategy for realizing the dual-channel sequential response on the basis of the progressively alterable nanomorphologies and emissions might provide deeper insights for the further development of advanced polymeric sensors. PMID:27275516

  4. All Solid State Rechargeable Lithium Batteries using Block Copolymers

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel; Balsara, Nitash

    2011-03-01

    The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

  5. Defect Structures in Block Copolymer/Nanoparticle Blends

    NASA Astrophysics Data System (ADS)

    Ryu, Hyung Ju; Bockstaller, Michael

    2009-03-01

    We present a systematic study of the implications of nanoparticle additives on the defect formation in block copolymer/nanoparticle blends (BCP). The morphology of lamellar styrene/isoprene-based di- and triblock copolymers blended with polystyrene-coated gold nanocrystals at various filling fractions was analyzed using electron microscopy using stereology and image reconstruction. Three structural characteristics, i.e. the grain size distribution, grain orientation distribution and grain boundary structure, were analyzed as a function of polymer chain architecture, particle filling fraction and film processing conditions. With increasing particle filling fraction the average anisotropy as well as average grain size is observed to decrease as is the rate of grain growth during thermal annealing. The results are interpreted in terms of the stabilization of grain boundary structures through segregation of particle fillers to the grain boundary regions.

  6. Bragg Reflectors Based on Block Copolymer/Polyhedral Oligomeric Silsesquioxanes (POSS) and TiO2 Hybrid Nanocomposites

    NASA Astrophysics Data System (ADS)

    Li, Cheng; Colella, Nicholas; Watkins, James

    2014-03-01

    Maleamic acid functionalized polyhedral oligomeric silsesquioxanes (POSS) can interact with the poly (ethylene oxide) (PEO) block in Pluronics F108 block copolymer via hydrogen bonding to form well-ordered block copolymer nanocomposites. In this study, the block copolymer composites are spin coated into thin films and maleamic acid groups are thermal crosslinked to stabilize the nanocomposite structure. High temperature calcination of the stabilized nanocomposite yields a robust mesoporous silica thin film. By adjusting the loading of POSS into the block copolymer prior to calcination, the refractive index (RI) of mesoporous silica films can be tuned between 1.13 and 1.18. We show these low RI films can be sequentially layered with hybrid TiO2 nanocomposite films that exhibit a RI of approximately 2.0 to yield efficient Bragg reflectors. The TiO2 films are prepared by the calcinations of polymer/anatase TiO2 nanoparticle composites with NP loadings as high as 90wt%. Due to the porosity existing in each layer, the wavelength of the reflected light is sensitive to the adsorption of solvent vapors such as toluene, isopropanol, and tetrahydrofuran, or analytes, which suggest applications in sensors. Acknowledge The Center for Hierarchical Manufacturing.

  7. Thermally-induced transition of lamellae orientation in block-copolymer films on ‘neutral’ nanoparticle-coated substrates

    DOE PAGESBeta

    Yager, Kevin G.; Forrey, Christopher; Singh, Gurpreet; Satija, Sushil K.; Page, Kirt A.; Patton, Derek L.; Jones, Ronald L.; Karin, Alamgir; Douglas, Jack F.

    2015-06-01

    Block-copolymer orientation in thin films is controlled by the complex balance between interfacial free energies, including the inter-block segregation strength, the surface tensions of the blocks, and the relative substrate interactions. While block-copolymer lamellae orient horizontally when there is any preferential affinity of one block for the substrate, we recently described how nanoparticle-roughened substrates can be used to modify substrate interactions. We demonstrate how such ‘neutral’ substrates can be combined with control of annealing temperature to generate vertical lamellae orientations throughout a sample, at all thicknesses. We observe an orientational transition from vertical to horizontal lamellae upon heating, as confirmedmore » using a combination of atomic force microscopy (AFM), neutron reflectometry (NR) and rotational small-angle neutron scattering (RSANS). Using molecular dynamics (MD) simulations, we identify substrate-localized distortions to the lamellar morphology as the physical basis of the novel behavior. In particular, under strong segregation conditions, bending of horizontal lamellae induce a large energetic cost. At higher temperatures, the energetic cost of conformal deformations of lamellae over the rough substrate is reduced, returning lamellae to the typical horizontal orientation. Thus, we find that both surface interactions and temperature play a crucial role in dictating block-copolymer lamellae orientation. As a result, our combined experimental and simulation findings suggest that controlling substrate roughness should provide a useful and robust platform for controlling block-copolymer orientation in applications of these materials.« less

  8. Thermally-induced transition of lamellae orientation in block-copolymer films on ‘neutral’ nanoparticle-coated substrates

    SciTech Connect

    Yager, Kevin G.; Forrey, Christopher; Singh, Gurpreet; Satija, Sushil K.; Page, Kirt A.; Patton, Derek L.; Jones, Ronald L.; Karin, Alamgir; Douglas, Jack F.

    2015-06-01

    Block-copolymer orientation in thin films is controlled by the complex balance between interfacial free energies, including the inter-block segregation strength, the surface tensions of the blocks, and the relative substrate interactions. While block-copolymer lamellae orient horizontally when there is any preferential affinity of one block for the substrate, we recently described how nanoparticle-roughened substrates can be used to modify substrate interactions. We demonstrate how such ‘neutral’ substrates can be combined with control of annealing temperature to generate vertical lamellae orientations throughout a sample, at all thicknesses. We observe an orientational transition from vertical to horizontal lamellae upon heating, as confirmed using a combination of atomic force microscopy (AFM), neutron reflectometry (NR) and rotational small-angle neutron scattering (RSANS). Using molecular dynamics (MD) simulations, we identify substrate-localized distortions to the lamellar morphology as the physical basis of the novel behavior. In particular, under strong segregation conditions, bending of horizontal lamellae induce a large energetic cost. At higher temperatures, the energetic cost of conformal deformations of lamellae over the rough substrate is reduced, returning lamellae to the typical horizontal orientation. Thus, we find that both surface interactions and temperature play a crucial role in dictating block-copolymer lamellae orientation. As a result, our combined experimental and simulation findings suggest that controlling substrate roughness should provide a useful and robust platform for controlling block-copolymer orientation in applications of these materials.

  9. Responsive Block Copolymer and Gold Nanoparticle Hybrid Nanotubes.

    NASA Astrophysics Data System (ADS)

    Chang, Sehoon; Singamaneni, Srikanth; Young, Seth; Tsukruk, Vladimir

    2009-03-01

    We demonstrate the facile fabrication of responsive polymer and metal nanoparticle composite nanotube structures. The nanotubes are comprised of responsive block copolymer, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and gold nanoparticles. PS-b-P2VP nanotubes were fabricated using porous alumina template and in situ reduction of the gold nanoparticles in P2VP domains. Owing to the pH sensitive nature of P2VP (anionic polymer with a pKa of 3.8), the nanotubes exhibit a dramatic change in topology in response to the changes in the external pH. Furthermore, the gold nanoparticles in the responsive block exhibit a reversible aggregation, causing a reversible change in optical properties such as absorption.

  10. Thin membranes of new hard/soft segment copolymers

    SciTech Connect

    Ho, W.S.; Sartori, G.; Thaler, W.A.

    1996-12-31

    Thin membranes of new hard/soft segment copolymers have been synthesized for the separation of aromatics from saturates through high temperature pervaporation. In the membranes, hard segments provide temperature stability and solvent resistance, while soft segments govern aromatic/saturate selectivity and flux. We have synthesized new chlorinated polyurethane/polyester and polyimide/polyester copolymers. Based on a polyimide copolymer membrane, a new technology has been developed recently to separate heavy catalytically cracked naphtha into an aromatics-rich permeate and an aromatics-lean retentate.

  11. Tetragonal Ordering in Block Copolymer-Homopolymer Blend Films Laterally Confined in a Square Well

    NASA Astrophysics Data System (ADS)

    Hur, Su-Mi; García-Cervera, Carlos; Kramer, Ed; Fredrickson, Glenn

    2009-03-01

    Self-consistent field theory (SCFT) simulations are presented for a melt blend of AB diblock copolymers and A homopolymers in a thin film confined to a square well. The work aims to guide self-assembly towards tetragonal ordering, which is a pattern of technological interest in block copolymer lithography. By using suitable A homopolymer additives, we have succeeded in achieving square lattices of cylinders not observed in the confined or bulk pure diblock system. A phase diagram is presented that shows the region of stability of the tetragonal phase as a function of chain length and volume fraction of the homopolymer additive, in addition to several other interesting phases that result from a competition between surface and bulk contributions to the free energy. Results are also presented on the effect of line edge roughness in the square confinement well on the achievement of robust and defect free tetragonal order.

  12. Periodic nanoscale patterning of polyelectrolytes over square centimeter areas using block copolymer templates.

    PubMed

    Oded, Meirav; Kelly, Stephen T; Gilles, Mary K; Müller, Axel H E; Shenhar, Roy

    2016-05-18

    Nano-patterned materials are beneficial for applications such as solar cells, opto-electronics, and sensing owing to their periodic structure and high interfacial area. Here, we present a non-lithographic approach for assembling polyelectrolytes into periodic nanoscale patterns over cm(2)-scale areas. Chemically modified block copolymer thin films featuring alternating charged and neutral domains are used as patterned substrates for electrostatic self-assembly. In-depth characterization of the deposition process using spectroscopy and microscopy techniques, including the state-of-the-art scanning transmission X-ray microscopy (STXM), reveals both the selective deposition of the polyelectrolyte on the charged copolymer domains as well as gradual changes in the film topography that arise from further penetration of the solvent molecules and possibly also the polyelectrolyte into these domains. Our results demonstrate the feasibility of creating nano-patterned polyelectrolyte layers, which opens up new opportunities for structured functional coating fabrication. PMID:27104854

  13. Self-assembly of block copolymers on topographically patterned polymeric substrates

    DOEpatents

    Russell, Thomas P.; Park, Soojin; Lee, Dong Hyun; Xu, Ting

    2016-05-10

    Highly-ordered block copolymer films are prepared by a method that includes forming a polymeric replica of a topographically patterned crystalline surface, forming a block copolymer film on the topographically patterned surface of the polymeric replica, and annealing the block copolymer film. The resulting structures can be used in a variety of different applications, including the fabrication of high density data storage media. The ability to use flexible polymers to form the polymeric replica facilitates industrial-scale processes utilizing the highly-ordered block copolymer films.

  14. Complex microstructures of ABC triblock copolymer thin films directed by polymer brushes based on self-consistent field theory.

    PubMed

    Jiang, Zhibin; Xu, Chang; Qiu, Yu Dong; Wang, Xiaoliang; Zhou, Dongshan; Xue, Gi

    2014-01-01

    The morphology and the phase diagram of ABC triblock copolymer thin film directed by polymer brushes are investigated by the self-consistent field theory in three dimensions. The polymer brushes coated on the substrate can be used as a good soft template to tailor the morphology of the block copolymer thin films compared with those on the hard substrates. The polymer brush is identical with the middle block B. By continuously changing the composition of the block copolymer, the phase diagrams are constructed for three cases with the fixed film thickness and the brush density: identical interaction parameters, frustrated and non-frustrated cases. Some ordered complex morphologies are observed: parallel lamellar phase with hexagonally packed pores at surfaces (LAM3 (ll) -HFs), perpendicular lamellar phase with cylinders at the interface (LAM(⊥)-CI), and perpendicular hexagonally packed cylinders phase with rings at the interface (C2 (⊥)-RI). A desired direction (perpendicular or parallel to the coated surfaces) of lamellar phases or cylindrical phases can be obtained by varying the composition and the interactions between different blocks. The phase diagram of ABC triblock copolymer thin film wetted between the polymer brush-coated surfaces is very useful in designing the directed pattern of ABC triblock copolymer thin film. PMID:25114650

  15. Surfaces of Fluorinated Pyridinium Block Copolymers with Enhanced Antibacterial Activity

    SciTech Connect

    Krishnan,S.; Ward, R.; Hexemer, A.; Sohn, K.; Lee, K.; Angert, E.; Fischer, D.; Kramer, E.; Ober, C.

    2006-01-01

    Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

  16. Gamma radiation induced degradation in PE-PP block copolymer

    NASA Astrophysics Data System (ADS)

    Ravi, H. R.; Sreepad, H. R.; Ahmed, Khaleel; Govindaiah, T. N.

    2012-06-01

    In the present investigation, effect of gamma irradiation on the PP-PE block copolymer has been studied. The polymer has been subjected to gamma irradiation from 100 to 500 Mrad dosages. Characterization of the polymer using XRD and FTIR was done both before irradiation and after irradiation in each step. Effect of irradiation on the electrical properties of the material has also been studied. FTIR study shows that the sample loses C - C stretching mode of vibration but gains C=C stretching mode of vibration after irradiation. Present investigation clearly indicates that though the electrical conductivity increases in the material, it undergoes degradation and shows brittleness due to irradiation.

  17. Structural investigations of block copolymer melts and solutions

    NASA Astrophysics Data System (ADS)

    Kossuth, Mary Beth

    1999-11-01

    Block copolymers have been observed to spontaneously self-assemble into a variety of ordered liquid crystalline phases, much like surfactant and lipid solutions. Among these structures are two cubic morphologies: spheres packed on a body-centered cubic lattice and a bicontinuous structure known as the gyroid. The viscoelastic behavior of these two microstructures was examined in detail for nine chemically distinct systems using oscillatory shear. Remarkable similarities were seen in the rheological responses of the two phases, and a universal picture of the viscoelastic behavior of cubic phases was proposed. Two features were observed in every system: a low frequency crossover of the storage and loss moduli, oxx, and a frequency independent plateau in the storage modulus, Gcubic°. The plateau modulus is related experimentally to the characteristic domain spacing d* of the microstructures by Gcubic °˜d*-3, while theory predicts a d*-2 dependence. There are similarities between the phase behavior of melt-state block copolymers and surfactant solutions both in the phases that appear and the order in which they occur. The phase behavior for a series of low molecular weight block copolymers of poly(ethylene oxide)-poly(ethyl ethylene) (PEO-PEE) was examined in the presence of water and both water and dodecane (oil) using small-angle x-ray scattering. In the binary aqueous solutions, phase behavior similar to that of nonionic surfactants was observed, with evidence of lamellae, hexagonally packed cylinders, and body-centered cubic spheres; however, no gyroid phase was seen. The phases were remarkably robust; ordered structures persisted even to high temperatures. Above a critical concentration only lyotropic phase behavior was seen; below this composition thermotropic behavior was evident. Addition of dodecane to a symmetric block copolymer produced a very different phase diagram than its aqueous counterpart. Face-centered cubic spheres and a small window of the

  18. Gamma radiation induced degradation in PE-PP block copolymer

    SciTech Connect

    Ravi, H. R.; Sreepad, H. R.; Ahmed, Khaleel; Govindaiah, T. N.

    2012-06-05

    In the present investigation, effect of gamma irradiation on the PP-PE block copolymer has been studied. The polymer has been subjected to gamma irradiation from 100 to 500 Mrad dosages. Characterization of the polymer using XRD and FTIR was done both before irradiation and after irradiation in each step. Effect of irradiation on the electrical properties of the material has also been studied. FTIR study shows that the sample loses C - C stretching mode of vibration but gains C=C stretching mode of vibration after irradiation. Present investigation clearly indicates that though the electrical conductivity increases in the material, it undergoes degradation and shows brittleness due to irradiation.

  19. Melt-Miscibility in Block Copolymers Containing Polyethylene and Substituted Polynorbornene Blocks

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    2015-03-01

    Block copolymers containing a crystallizable block, such as polyethylene (PE), and a high-Tg amorphous block are potentially interesting materials since the rigid glassy block can mitigate the poor yield strength of the PE crystals. However, chemical incompatibility between blocks, quantified by the Flory interaction parameter χ or the interaction energy density X, drives microphase separation at low temperatures or high chain lengths. To prepare a high molecular weight PE-containing block copolymer that is easy to process (i.e. with a disordered low-viscosity melt) it is necessary to select amorphous blocks that have low mixing energies with PE. The only suitable polymers currently known are chemically similar to PE and therefore have similarly low glass transition temperatures. We investigate a series of both low- and high-Tg polymers based on substituted norbornene monomers, polymerized via ring-opening metathesis polymerization (ROMP). Several ROMP polymers of this type exhibit high Tg and low interaction energy against PE. For example, hydrogenated poly(cyclohexyl norbornene) has Tg = 88 oC and has interaction energy density XhPCyN - PE ~ 0.8 MPa, comparable to the interaction energy density between PE and hydrogenated polyisoprene. The miscibility of an amorphous block can be further tuned by statistical copolymerization of norbornene units with aromatic side-groups (high Hildebrand solubility parameter) and norbornene units with aliphatic side-groups (low Hildebrand solubility parameter).

  20. In-situ SAXS observation of magnetic field effects on block copolymer ordering and alignment

    NASA Astrophysics Data System (ADS)

    Osuji, Chinedum; Gopinadhan, Manesh; Majewksi, Pawel

    2012-02-01

    The use of external fields to direct block copolymer self-assembly is well documented. Magnetic fields offer particular promise due to their space-pervasive nature and the ability to produce arbitrary alignments over truly macroscopic length scales in appropriate systems. We present here the results of in-situ SAXS studies of side-chain liquid crystalline diblock copolymers ordering under high magnetic fields and ex-situ GISAXS data on thin films. Despite the coincidence of the block copolymer order-disorder transition (ODT) and the LC clearing temperature in these weakly segregated materials, there is no measurable effect of the field on the ODT of the system, up to 6 T. This is in line with rough estimates based simply on the magnitudes of the relevant energy scales - the free energy of field interaction and the enthalpy of the isotropic-LC transition. We show that the alignment of the system is critically limited by the viscosity of the mesophase such that alignment can only be advanced by residence in a small temperature window near TODT. This residence produces a weakly aligned system which thereafter transitions to a strongly aligned state on cooling even in the absence of the field.

  1. Determination of molecular-weight distribution and average molecular weights of block copolymers by gel-permeation chromatography.

    PubMed

    Nesterov, V V; Kurenbin, O I; Krasikov, V D; Belenkii, B G

    1987-01-01

    The problem of preparation of a block copolymer of precise molecular-weight distribution (MWD) and with heterogeneous composition on the basis of gel-permeation chromatography (GPC) data has been investigated. It has been shown that in MWD calculations the distribution f(p) of the composition p in individual GPC fractions should be taken into account. The type of the f(p) functions can be simultaneously established by an independent method, such as use of adsorption-column or thin-layer chromatography sensitive to the composition of the copolymer. It has also been shown that the actual f(p) may be replaced by a corresponding piecewise distribution, of simple form, without decrease in the precision of calculation of the MWD and average molecular weights of most known block copolymers. PMID:18964273

  2. Controlling thermochromism in a photonic block copolymer gel.

    PubMed

    Walish, Joseph J; Fan, Yin; Centrone, Andrea; Thomas, Edwin L

    2012-09-26

    The tunable properties of stimulus-responsive materials attract great interest in a variety of technological applications. Photonic gels are a new class of these materials, which can be tuned to reflect different wavelengths of light. Controlling this reflected color via temperature-induced changes of self-assembled photonic materials is important for their application in sensors and displays. In this work, the thermochromic behavior of a PS-P2VP photonic gel was found to originate from a temperature-induced change in the pK(a) of the P2VP blocks. Control was obtained through the manipulation of the solution pH. The findings of this work provide the basis for understanding and controlling the properties of thermochromic block copolymers fostering their use in technologically relevant applications. PMID:22763921

  3. Characterizing the interfaces of block copolymers with high χ

    NASA Astrophysics Data System (ADS)

    Sunday, Daniel; Maher, Michael; Blachut, Gregory; Asano, Yusuke; Tein, Summer; Willson, C. Grant; Ellison, Christopher; Kline, R. Joseph

    In order for block copolymer (BCP) directed self-assembly (DSA) to be able to pattern features below 10 nm there must be materials which can spontaneously assembly at the required length scales. For the smallest features this will require phase separation where the total chain lengths are under 50 monomer units, demanding very large interaction parameters (χ) to have an order-disorder transition. One of the key parameters for DSA will be the interfacial width between the blocks, which is expected to be correlated to the interaction parameter and will help determine the line edge roughness (LER). We have used resonant soft X-ray reflectivity to investigate a series of high χ BCPs with different compositions and molecular weights to determine the interfacial width and degree of phase separation. We use these results to estimate the value of χ and determine relationships between χ and the interfacial mixing.

  4. Chirality in block copolymer melts: mesoscopic helicity from intersegment twist.

    PubMed

    Zhao, Wei; Russell, Thomas P; Grason, Gregory M

    2013-02-01

    We study the effects of chirality at the segment scale on the thermodynamics of block copolymer melts using self-consistent field theory. In linear diblock melts where segments of one block prefer a twisted, or cholesteric, texture, we show that melt assembly is critically sensitive to the ratio of random coil size to the preferred pitch of cholesteric twist. For weakly chiral melts (large pitch), mesophases remain achiral, while below a critical value of pitch, two mesoscopically chiral phases are stable: an undulated lamellar phase and a phase of hexagonally ordered helices. We show that the nonlinear sensitivity of mesoscale chiral order to preferred pitch derives specifically from the geometric and thermodynamic coupling of the helical mesodomain shape to the twisted packing of chiral segments within the core, giving rise to a second-order cylinder-to-helix transition. PMID:23414052

  5. Morphological evolution of lamellar forming polystyrene-block-poly(4-vinylpyridine) copolymers under solvent annealing.

    PubMed

    Ghoshal, Tandra; Chaudhari, Atul; Cummins, Cian; Shaw, Matthew T; Holmes, Justin D; Morris, Michael A

    2016-06-28

    In this work, we are reporting a very simple and efficient method to form lamellar structures of symmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymer thin films with vertically (to the surface plane) orientated lamellae using a solvent annealing approach. The methodology does not require any brush chemistry to engineer a neutral surface and it is the block neutral nature of the film-solvent vapour interface that defines the orientation of the lamellae. The microphase separated structure of two different molecular weight lamellar forming PS-block-P4VP copolymers formed under solvent vapour annealing was monitored using atomic force microscopy (AFM) so as to understand the morphological changes of the films upon different solvent exposure. In particular, the morphology changes from micellar structures to well-defined microphase separated arrangements. The choice of solvent/s (single and dual solvent exposure) and the solvent annealing conditions (temperature, time etc.) has important effects on structural transitions of the films and it was found that a block neutral solvent was required to realize vertically aligned P4VP lamellae. The results of the structural variation of the phase separated nanostructured films through the exposure to ethanol are also described. PMID:27240904

  6. Transport of Water in Semicrystalline Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel; Oparaji, Onyekachi

    Poly(styrene)-block-poly(ethylene oxide) (PS- b-PEO) is a semicrystalline block copolymer (BCP) with interesting properties. It is mechanically tough, amphiphilic, and has a polar phase. The mechanical toughness is due to the crystallinity of PEO and the high glass transition temperature of PS, as well as the morphological structure of the BCP. The polymer has high CO2, water, and salt solubility that derive from the polar PEO component. Potential applications include CO2 separation, water purification, and lithium air batteries. In all of the aforementioned applications, water transport is an important parameter. The presence of water can also affect thermal and mechanical properties. Water transport and thermal and mechanical properties of a lamellar PS- b-PEO copolymer have been measured as a function of water activity. Water transport can be affected by the heterogeneous nature of a semicrystalline BCP. Therefore, Fourier transform infrared - attenuated total reflectance (FTIR-ATR) spectroscopy has been employed, because water transport and polymer swelling can be measured simultaneously. The effect of BCP structure on transport has been investigated by comparing water transport in PS- b-PEO to a PEO homopolymer. The crystalline content of the PEO and the presence of glassy PS lamellae will be used to explain the transport results.

  7. Single Helix to Double Gyroid in Chiral Block Copolymers

    SciTech Connect

    C Chen; H Hsueh; Y Chiang; R Ho; S Akasaka; H Hasegawa

    2011-12-31

    An order-order phase transition of chiral block copolymers (BCPs*) from single helix to double gyroid (H* {yields} G) through a nucleation and growth process was demonstrated. The H* and G phases can be obtained by solution casting from fast and slow solvent evaporation, respectively, suggesting that the H* phase is a metastable phase. Consequently, the coexistence of H* and G phases can be found in the solution-cast samples from intermediate solvent evaporation. To truly examine the transition mechanism of the H* {yields} G, electron tomography was carried out to directly visualize the morphological evolution in real space, in particular, the transition zone at interface. Unlike the mechanisms for the transitions of block copolymers (BCPs) by considering the interdomain spacing matching, a significant mismatch in the lattices for the H* {yields} G was found. Consequently, the transition may require an adjustment on the geometric dimensions to justify corresponding lattice mismatch. As a result, the morphological observations from electron tomography offer new insights into BCP phase transitions.

  8. Synthesis and antibacterial activity of nisin-containing block copolymers.

    PubMed

    Joshi, Pranav R; McGuire, Joseph; Neff, Jennifer A

    2009-10-01

    Nisin, an antibacterial peptide proven to be an effective inhibitor of Gram-positive bacteria, was incorporated into novel block copolymer constructs and tested for retained antibacterial activity. Covalent coupling was achieved by chemical modification of the N-terminal isoleucine to introduce a thiol group. Thiolated-nisin derivatives were then linked to poly[ethylene oxide]-poly[propylene oxide]-poly[ethylene oxide] (PEO-PPO-PEO) triblocks that had been end-activated such that terminal hydroxyl groups of the PEO chains were replaced with pyridyl disulfide moieties. The nisin-containing block copolymers were separated from free nisin by dialysis and showed antimicrobial activity against the Gram-positive indicator strain Pediococcus pentosaceus. The contribution to antimicrobial activity from nisin that was covalently linked was not distinguished from the contribution of nisin that had associated with the PEO-PPO-PEO triblocks through noncovalent interactions. However, nisin that was covalently linked showed activity upon reduction of the disulfide bond and release from the end-activated PEO. PMID:19358262

  9. Making Carbon-Nanotube Arrays Using Block Copolymers: Part 2

    NASA Technical Reports Server (NTRS)

    Bronikowski, Michael

    2004-01-01

    Some changes have been incorporated into a proposed method of manufacturing regular arrays of precisely sized, shaped, positioned, and oriented carbon nanotubes. Such arrays could be useful as mechanical resonators for signal filters and oscillators, and as electrophoretic filters for use in biochemical assays. A prior version of the method was described in Block Copolymers as Templates for Arrays of Carbon Nanotubes, (NPO-30240), NASA Tech Briefs, Vol. 27, No. 4 (April 2003), page 56. To recapitulate from that article: As in other previously reported methods, carbon nanotubes would be formed by decomposition of carbon-containing gases over nanometer-sized catalytic metal particles that had been deposited on suitable substrates. Unlike in other previously reported methods, the catalytic metal particles would not be so randomly and densely distributed as to give rise to thick, irregular mats of nanotubes with a variety of lengths, diameters, and orientations. Instead, in order to obtain regular arrays of spaced-apart carbon nanotubes as nearly identical as possible, the catalytic metal particles would be formed in predetermined regular patterns with precise spacings. The regularity of the arrays would be ensured by the use of nanostructured templates made of block copolymers.

  10. Self-assembled diblock copolymer thin films for the analysis of bacteria-surface interactions

    NASA Astrophysics Data System (ADS)

    Li, Shuyan; Komaromy, Andras; Boysen, Reinhard I.; Nicolau, Dan V.; Hearn, Milton T. W.

    2008-12-01

    Self-assembling polymers have recently attracted significant scientific interest, since they spontaneously generate highly ordered structures with high resolution precision, and provide simple, parallel, and cost-effective processes for nanofabrication. Such systems can be achieved with block copolymers which, when produced as thin films, offer great potential as lithographic templates for the fabrication of photonic band-gap materials, ultrahigh-density nanodots or nanowire arrays, memory and capacitor devices, and nano-patterned substrates for biosensors. Although self-assembling block copolymers can form a variety of surface topographies at the nm scale, like spheres, cylinders, and lamellae, their structural steering through the annealing conditions has in many cases not been fully investigated. In the present investigation optimum production conditions for the preparation of nanostructures from poly(styrene)-block-poly(MMA) diblock copolymers have been established to enable the production of surfaces as thin films (<40 nm) on spin-coated silicon wafers either with parallel cylindrical structures or with vertical cylinders. The resulting self-assembling structures were then evaluated by atomic force microscopy. The obtained nanostructured polymers were then incubated with two microbial species, the gram negative E. coli and the gram positive S. aureus to assess their behaviour. The patterns of the thin film surfaces affected the bacterial attachment. Such self assembly processes can be used to create surfaces acting as bacterial attractants or repellents.

  11. Self-Organization on Multiple Length Scales in ``Hairy-Rod''--Coil Block Copolymer Supramolecular Complexes

    NASA Astrophysics Data System (ADS)

    Mezzenga, Raffaele; Hammond, Matthew; Klok, Harm-Anton

    2008-03-01

    A peptide-synthetic hybrid block copolymer, poly(ethylene oxide)-block-poly(L-glutamic acid), is demonstrated to form supramolecular complexes with primary alkylamines of varying alkyl chain length (8 to 18 methylene units) in organic solvents via acid-base proton transfer and subsequent ionic bonding. The peptidic block being in the α-helical conformation, these materials behave as coil-``hairy rod'' block copolymers, and show hierarchically self-organized nanostructures in the solid state; X-ray scattering measurements show mesomorphic behavior at the length scales of both the overall block copolymer and the polypeptide-alkylammonium complex.

  12. Effect of nanoscale morphology on selective ethanol transport through block copolymer membranes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We report on the effect of block copolymer domain size on transport of liquid mixtures through the membranes by presenting pervaporation data of an 8 wt% ethanol/water mixture through A-B-A and B-A-B triblock copolymer membranes. The A-block was chosen to facilitate ethanol transport while the B-blo...

  13. Hierarchical Manipulation of Block Copolymer Patterns on 3D Topographic Substrates: Beyond Graphoepitaxy.

    PubMed

    Park, Sungjune; Cheng, Xiao; Böker, Alexander; Tsarkova, Larisa

    2016-08-01

    Templates of complex nanopatterns in a form of hierarchically sequenced dots and stripes can be generated in block copolymer films on lithography-free 3D topographic substrates. The approach exploits thickness- and swelling-responsive morphological behavior of block copolymers, and demonstrates novel possibilities of topography-guided registration of nanopatterns due to periodic confinement and spontaneous orthogonal flow-fields. PMID:27270877

  14. Master curve captures the effect of domain morphology on ethanol pervaporation through block copolymer membranes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We report on the effect of changing nanoscale morphology on pervaporation of ethanol/water mixtures through block copolymer membranes. Experiments were conducted using polystyrene-b-polybutadiene-b-polystyrene (SBS) copolymers with polybutadiene (PB) as the ethanol transporting block, using an 8 wt%...

  15. Phase behavior of multi-arm star-shaped polystyrene-block-poly(methyl methacrylate) copolymer

    NASA Astrophysics Data System (ADS)

    Jang, Sangshin; Moon, Hong Chul; Bae, Dusik; Kwak, Jonghen; Kim, Jin Kon

    2013-03-01

    We synthesized star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS- b-PMMA) by utilizing α-cyclodextrin (α-CD) as a core of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were transformed to bromine by the reaction with α-bromoisobutyryl bromide. We found that the number of bromine substituted arms per one α-CD was higher than 16, which was determined by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of block copolymers by changing polymerization times. The block copolymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behaviors of these star-shaped block copolymers were investigated by small angle X-ray scattering and transmission electron microscopy.

  16. Understanding the ordering mechanisms of self-assembled nanostructures of block copolymers during zone annealing

    NASA Astrophysics Data System (ADS)

    Cong, Zhinan; Zhang, Liangshun; Wang, Liquan; Lin, Jiaping

    2016-03-01

    A theoretical method based on dynamic version of self-consistent field theory is extended to investigate directed self-assembly behaviors of block copolymers subjected to zone annealing. The ordering mechanisms and orientation modulation of microphase-separated nanostructures of block copolymers are discussed in terms of sweep velocity, wall preference, and Flory-Huggins interaction parameter. The simulated results demonstrate that the long-range ordered nanopatterns are achieved by lowering the sweep velocity of zone annealing due to the incorporation of templated ordering of block copolymers. The surface enrichment by one of the two polymer species induces the orientation modulation of defect-free nanostructures through finely tuning the composition of block copolymers and the preference of walls. Additionally, the Flory-Huggins interaction parameters of block copolymers in the distinct regions are main factors to design the zone annealing process for creating the highly ordered nanostructures with single orientation.

  17. Protonation-Induced Microphase Separation in Thin Films of a Polyelectrolyte-Hydrophilic Diblock Copolymer

    PubMed Central

    2015-01-01

    Block copolymers composed of poly(oligo ethylene glycol methyl ether methacrylate) and poly(2-vinylpyridine) are disordered in the neat state but can be induced to order by protonation of the P2VP block, demonstrating a tunable and responsive method for triggering assembly in thin films. Comparison of protonation with the addition of salts shows that microphase separation is due to selective protonation of the P2VP block. Increasing acid incorporation and increasing 2-vinylpyridine content for P2VP minority copolymers both promote increasingly phase-separated morphologies, consistent with protonation increasing the effective strength of segregation between the two blocks. The self-assembled nanostructures formed after casting from acidic solutions may be tuned based on the amount and type of acid incorporation as well as the annealing treatment applied after casting, where both aqueous and polar organic solvents are shown to be effective. Therefore, POEGMA-b-P2VP is a novel ion-containing block copolymer whose morphologies can be facilely tuned during casting and processing by controlling its exposure to acid. PMID:24910809

  18. New routes to the synthesis of amylose-block-polystyrene rod-coil block copolymers.

    PubMed

    Loos, Katja; Müller, Axel H E

    2002-01-01

    Hybrid block copolymers amylose-block-polystyrene were synthesized by covalent attachment of maltoheptaose derivatives to end-functionalized polystyrene and subsequent enzymatic grafting from polymerization. The maltoheptaose derivatives were attached by reductive amination or hydrosilation to amino- or SiH-terminated polystyrene (synthesized by anionic polymerization), respectively. The enzymatic polymerization could be started even though the primer-modified polystyrenes were insoluble in the medium of polymerization, i.e., citrate buffer. The polymerization kinetics show an interesting dependence on the molecular weight of polystyrene due to the micellar structure of the primer in water. PMID:11888324

  19. Nanowire polarizers by guided self-assembly of block copolymers

    NASA Astrophysics Data System (ADS)

    Roberts, Philip M. S.; Baum, Alexandra; Karamath, James; Evans, Allan; Shibata, Satoshi; Walton, Harry

    2014-01-01

    Wire-grid polarizers (WGPs) are currently limited by their wafer-scale manufacturing methods to sizes of approximately 12 to 18 in. For large-size displays, a new method for the production of large-area WGPs is required. Large-area WGPs were simulated using the finite-difference-time-domain method, and a scaleable method for their production based on a block copolymer (BCP)-nanostructured template was implemented. The nanostructured template is globally aligned through the use of a cylinder-forming liquid crystal (LC) diblock copolymer, which is first aligned on a rubbed polyimide substrate. A surface-relief template is produced using the differential dry etch rates of the cylinder-forming component and LC polymer matrix component of the BCP. The template is metalized to produce a WGP. Polarizers of arbitrary size with polarization efficiency up to 0.6 have been made in close agreement with calculated values for idealized structures. The choice of the cylinder-forming polymer is critical to the degree of alignment of the template, and the thermal stability of the LC polymer matrix is critical to the stability of the template during etching.

  20. Ultrathin and Micellar Block Copolymer Films for Nanopatterning

    NASA Astrophysics Data System (ADS)

    Möller, Martin

    1998-03-01

    The formation of A-B functionalized surfaces, where nanometer sized A and B patches are distinguished for their different physical and chemical properties, represent a rather virgin field of research. We will present a technology for generating nanosized chemical heterogeneous surfaces by combination of self-organization of metal particle containing diblock copolymer micelles and conventional semiconductor etching techniques. Polystrene-block-poly(2-vinylpyridine) diblock copolymers form reverse micelles in toluene, i.e., a core of P2VP is protected by a shell of PS. Such nanocompartments are used for generating metal or semiconductor particles of equal size in each single micelle in solution. The micelle stabilized particles can be cast to mono micellar films, forming quasi hexagonal arranged lattices. The particle to particle distance (10 to 200nm) is controlled by the polymer shell and the particles size (1 to 20nm) by the micellar compartment. After film formation the polymer shell can be removed comp letely by using an oxygen plasma technique resulting in the deposition of the naked clusters on different substrates without destroying the former particle organization. These highly regular metal or semiconducting nanopatches can cover macroscopic areas (5cm x 5cm). The metal patterns are used for binding single makromolecules or as masks for nanolithography. Epitaxially grown semiconductors like GaAs, InGaAs or InP have been structured by islands or holes and their quantisized band structure has been in vestigated.

  1. Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

    SciTech Connect

    Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; Yager, Kevin G.; Strzalka, Joseph; Nie, Wanyi; Mohite, Aditya D.; Verduzco, Rafael

    2015-11-03

    All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor-block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we show that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.

  2. Negative-tone block copolymer lithography by in situ surface chemical modification.

    PubMed

    Kim, Bong Hoon; Byeon, Kyeong-Jae; Kim, Ju Young; Kim, Jinseung; Jin, Hyeong Min; Cho, Joong-Yeon; Jeong, Seong-Jun; Shin, Jonghwa; Lee, Heon; Kim, Sang Ouk

    2014-10-29

    Negative-tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self-assembled nanopatterning. BCP blends films consisting of end-functionalized low molecular weight poly(styrene-ran-methyl methacrylate) and polystyrene-block-Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end-functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self-assembled nanodomain formation facilitates single step, site-specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self-assembly approaches to produce device oriented laterally ordered nanopatterns. PMID:24912807

  3. Anion conductive aromatic block copolymers containing diphenyl ether or sulfide groups for application to alkaline fuel cells.

    PubMed

    Yokota, Naoki; Ono, Hideaki; Miyake, Junpei; Nishino, Eriko; Asazawa, Koichiro; Watanabe, Masahiro; Miyatake, Kenji

    2014-10-01

    A novel series of aromatic block copolymers composed of fluorinated phenylene and biphenylene groups and diphenyl ether (QPE-bl-5) or diphenyl sulfide (QPE-bl-6) groups as a scaffold for quaternized ammonium groups is reported. The block copolymers were synthesized via aromatic nucleophilic substitution polycondensation, chloromethylation, quaternization, and ion exchange reactions. The block copolymers were soluble in organic solvents and provided thin and bendable membranes by solution casting. The membranes exhibited well-developed phase-separated morphology based on the hydrophilic/hydrophobic block copolymer structure. The membranes exhibited mechanical stability as confirmed by DMA (dynamic mechanical analyses) and low gas and hydrazine permeability. The QPE-bl-5 membrane with the highest ion exchange capacity (IEC = 2.1 mequiv g(-1)) exhibited high hydroxide ion conductivity (62 mS cm(-1)) in water at 80 °C. A noble metal-free fuel cell was fabricated with the QPE-bl-5 as the membrane and electrode binder. The fuel cell operated with hydrazine as a fuel exhibited a maximum power density of 176 mW cm(-2) at a current density of 451 mA cm(-2). PMID:25215564

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

    PubMed

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

    2015-06-17

    We demonstrate glancing-angle deposition of gold on a nanostructured diblock copolymer, namely polystyrene-block-poly(methyl methacrylate) thin film. Exploiting the selective wetting of gold on the polystyrene block, we are able to fabricate directional hierarchical structures. We prove the asymmetric growth of the gold nanoparticles and are able to extract the different growth laws by in situ scattering methods. The optical anisotropy of these hierarchical hybrid materials is further probed by angular resolved spectroscopic methods. This approach enables us to tailor functional hierarchical layers in nanodevices, such as nanoantennae arrays, organic photovoltaics, and sensor electronics. PMID:25635697

  5. Structure-property relationships in multilayered polymeric system and olefinic block copolymers

    NASA Astrophysics Data System (ADS)

    Khariwala, Devang

    diffusion. Subsequently, the oxygen permeability was directly related to the composition profile in each layer and changed as the interdiffusion proceeded. This methodology enabled the extraction of the mutual diffusion co-efficient, D, for the Nylon-6/EVOH system. The effect of comonomer content in EVOH on the mutual diffusion coefficient was also studied by comparing the kinetics of interdiffusion of Nylon-6 with two EVOHs containing 24 and 44 mole % ethylene. Chapter 3. Exciting new developments in polyolefin synthesis give rise to olefinic block copolymers with properties typical of thermoplastic elastomers. The block copolymers synthesized by chain shuttling technology consist of crystallizable ethylene-octene blocks with low comonomer content and high melting temperature (hard blocks), alternating with amorphous ethylene-octene blocks with high comonomer content and low glass transition temperature (soft blocks). This study describes the material science of these unique polymers as characterized by thermal analysis, X-ray diffraction, microscopy, and tensile deformation. The crystallizable blocks are long enough to form well-organized lamellar crystals with the orthorhombic unit cell and high melting temperature. The lamellae are organized into space-filling spherulites in all compositions even in copolymers with only 18 wt% hard block. The morphology is consistent with crystallization from a miscible melt. Crystallization of the hard blocks forces segregation of the noncrystallizable soft blocks into the interlamellar regions. Good separation of hard and soft blocks in the solid state is confirmed by distinct and separate beta- and alpha-relaxations in all the block copolymers. Compared to statistical ethylene-octene copolymers, the blocky architecture imparts a substantially higher crystallization temperature, a higher melting temperature and a better organized crystalline morphology, while maintaining a lower glass transition temperature. The differences between

  6. Sprayable Elastic Conductors Based on Block Copolymer Silver Nanoparticle Composites

    PubMed Central

    2015-01-01

    Block copolymer silver nanoparticle composite elastic conductors were fabricated through solution blow spinning and subsequent nanoparticle nucleation. The reported technique allows for conformal deposition onto nonplanar substrates. We additionally demonstrated the ability to tune the strain dependence of the electrical properties by adjusting nanoparticle precursor concentration or localized nanoparticle nucleation. The stretchable fiber mats were able to display electrical conductivity values as high as 2000 ± 200 S/cm with only a 12% increase in resistance after 400 cycles of 150% strain. Stretchable elastic conductors with similar and higher bulk conductivity have not achieved comparable stability of electrical properties. These unique electromechanical characteristics are primarily the result of structural changes during mechanical deformation. The versatility of this approach was demonstrated by constructing a stretchable light emitting diode circuit and a strain sensor on planar and nonplanar substrates. PMID:25491507

  7. Block copolymer films with free interfaces: Ordering by nanopatterned substrates

    NASA Astrophysics Data System (ADS)

    Man, Xingkun; Andelman, David; Orland, Henri

    2012-07-01

    We study block copolymers (BCPs) on patterned substrates, where the top polymer film surface is not constrained but is free and can adapt its shape self-consistently. In particular, we investigate the combined effect of free interface undulations with wetting of the BCP film as induced by nanopatterned substrates. Under wetting conditions and for a finite volume of BCP material, we find equilibrium droplets composed of coexisting perpendicular and parallel lamellar domains. The self-assembly of BCPs on topographic patterned substrates is also investigated and it is found that the free interface induces mixed morphologies of parallel and perpendicular domains coupled with a nonflat free interface. Our study has some interesting consequences for experimental setups of graphoepitaxy and nanoimprint lithography.

  8. Block copolymers useful for enhanced oil recovery processes

    SciTech Connect

    Shu, P.

    1989-10-03

    This patent describes a method for permeability control of a subterranean formation and for enhancing oil recovery from the subterranean formation. The method comprising injecting into the subterranean formation an aqueous solution comprised of a block copolymer having the structural form of ABA triblock or (AB){sub n} multiblock wherein A is a crosslinkable polymer, B is a non-crosslinkable polymer or a polymer having low reactivity to crosslinking agents, n is a number of at least 2 and a crosslinking agent. Wherein A is selected from the group consisting of polyacrylic acid, partially hydrolyzed polyacrylamide, highly hydrolyzed polyacrylamide, partially hydrolyzed polyacrylic ester, highly hydrolyzed polyacrylic ester, polyvinyl alcohol and mixtures thereof and B is selected from the group consisting of polyacrylamide, partially hydrolyzed polyacrylamide, polyalkylene ethers, polyvinyl alcohol and polyvinylpyridine.

  9. Microstructural organization of polydimethylsiloxane based polyurethane block copolymers

    NASA Astrophysics Data System (ADS)

    Hernandez, Rebeca; Weksler, Jadwiga; Padsalgikar, Ajay; Runt, James

    2007-03-01

    Microphase separation was investigated for polyurethane block copolymers synthesized from MDI and 1,4 butanediol as the hard segments, and poly(hexamethyleneoxide) (MW ˜ 700) and bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane) as soft segments (MW ˜ 1000). The neat PDMS-based diol presents two segmental relaxations corresponding to the principle siloxane repeat unit and to the hydroxyethoxypropyl end group segments, respectively. When incorporated in the polyurethane, the siloxane units form a phase without intermixing with hard segments and the polyether end group segments are mixed with the second macrodiol and some short hard segment sequences. The microdomain morphology was characterized by atomic force microscopy and small-angle X-ray scattering, and the scattering data were analyzed using an approach based on a modified core-shell model. The model includes core hard segment particles (MDI-BDO), surrounded by a mixed polyether shell (PHMO and hydroxyethoxypropyl end group segments), and a matrix composed of the siloxane units.

  10. Effects of depletion interactions on block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Abbas, Sayeed; Lodge, Timothy P.

    2008-03-01

    Block copolymer micelles exhibit two levels of hierarchical self-assembly: the process of micellization itself, and the ordering of these micelles onto a lattice. By a combination of small angle x-ray scattering and neutron scattering, we show that both levels of self-assembly are affected when non-adsorbing homopolymer is added to the solutions. The phenomena are analogous to depletion interactions in colloid/polymer mixtures. We have chosen poly(styrene-b-isoprene) micelles dissolved in diethyl phthalate as the model system. To these solutions polystyrene homopolymer was added. The effects strongly depend on the molecular weight and concentration of the added homopolymer. We find an induced attraction between micelles at moderate micelle concentrations, and a preference for fcc over bcc lattices in more concentrated solutions.

  11. Superlattice Formation in Binary Mixtures of Block Copolymer Micelles

    SciTech Connect

    Abbas, Sayeed; Lodge, Timothy P.

    2008-08-26

    Two distinct diblock copolymers, poly(styrene-b-isoprene) (SI) and poly(styrene-b-dimethylsiloxane) (SD), were codissolved at various concentrations in the polystyrene selective solvent diethyl phthalate. Two SI diblocks, with block molar masses of 12000-33000 and 30000-33000, and two SD diblocks, with block molar masses of 19000-6000 and 16000-9000, were employed. The size ratio of the smaller SD micelles (S) to the larger SI micelles (L) varied from approximately 0.5 to 0.6, based on hydrodynamic radii determined by dynamic light scattering on dilute solutions containing only one polymer component. Due to incompatibility between the polyisoprene and polydimethylsiloxane blocks, a binary mixture of distinct SI and SD micelles was formed in each mixed solution, as confirmed by cryogenic transmission electron microscopy. When the total concentration of polymer was increased to 20--30%, the micelles adopted a superlattice structure. Small angle X-ray scattering revealed the lattice to be the full LS{sub 13} superlattice (space group Fm{sub 3}c) in all cases, with unit cell dimensions in excess of 145 nm. A coexistent face-centered cubic phase composed of SD micelles was also observed when the number ratio of S to L micelles was large.

  12. Lamellae Orientation in Block Copolymer Films with Ionic Complexes

    SciTech Connect

    Wang,J.; Chen, W.; Sievert, J.; Russell, T.

    2008-01-01

    Lamellae orientation in lithium-complexed polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymer films on natively oxidized silicon wafers is investigated as a function of film thickness and percentage of carbonyl groups coordinated with lithium ions using cross-sectional transmission electron microscopy and grazing incidence small-angle X-ray scattering. For films with a lower percentage of ionic complexes, the strong surface interaction of the PMMA blocks with the substrate is not changed significantly and the orientation of the lamellar microdomains depends on the film thickness and is dictated by a coupling of the interfacial interactions and the degree of microphase separation. For films with a higher percentage of ionic complexes, the surface interaction is mediated. Along with the enhanced immiscibility between the two blocks, which drives the self-assembly into a stronger microphase segregation, an orientation of the lamellar microdomains normal to the surface is seen, independent of film thickness. Thus, by tuning the amount of ionic complexes, the orientation of lamellar microdomain can be controlled from a random arrangement to being oriented parallel or perpendicular to the film surface without any surface modification or use of external fields, which opens a simple and general route for the fabrication of nanostructured materials.

  13. Fullerene-grafted block copolymers used as compatibilizer in P3HT/PCBM bulk heterojunctions: morphology and photovoltaic performances

    NASA Astrophysics Data System (ADS)

    Gernigon, V.; Lévêque, P.; Brochon, C.; Audinot, J.-N.; Leclerc, N.; Bechara, R.; Richard, F.; Heiser, T.; Hadziioannou, G.

    2011-12-01

    The nanostructure of the active layer in polymer/fullerene bulk heterojunction solar cells is known to have a strong impact on the device performances. Controlling the polymer/fullerene blend morphology is therefore particularly important. In this work, a rod-coil block copolymer, based on a regioregular poly(3-hexylthiophene) electron-donor rod block and a C60-grafted coil block, is used as compatibilizer and its influences on the thin film morphology as well as the photovoltaic performances are investigated. It is shown that a small fraction of compatibilizer can enhance the device performances in an otherwise non-optimized process. At higher fractions or long annealing times however, the fullerene-grafted copolymer is found to behave as a nucleation center and triggers the formation of fullerene crystals.

  14. Tough Block Copolymer Organogels and Elastomers as Short Fiber Composites

    NASA Astrophysics Data System (ADS)

    Kramer, Edward J.

    2012-02-01

    The origins of the exceptional toughness and elastomeric properties of gels and elastomers from block copolymers with semicrystalline syndiotactic polypropylene blocks will be discussed. Using synchrotron X-radiation small angle (SAXS) and wide angle X-ray scattering (WAXS) experiments were simultaneously performed during step cycle tensile deformation of these elastomers and gels. From these results the toughness can be attributed to the formation, orientation and elongation of the crystalline fibrils along the tensile direction. The true stress and true strain ɛH during each cycle were recorded, including the true strain at zero load ɛH,p after each cycle that resulted from the plastic deformation of the sPP crystals in the gel or elastomer. The initial Young's modulus Einit and maximum tangent modulus Emax in each cycle undergo dramatic changes as a function of ɛH,p, with Einit decreasing for ɛH,p <= 0.1 and then increasing slowly as ɛH,p increases to 1 while Emax increases rapidly over the entire range of ɛH,p resulting in a ratio of Emax/Einit > 100 to 1000 at the highest maximum (nominal) strain. Based on SAXS patterns from the deformed and relaxed gels, as well as on previous results on deformation of semicrystalline random copolymers by Strobl and coworkers, we propose that the initial decrease in Einit and increase in Emax with ɛH,p are due to a breakup of the network of the original sPP crystal lamellae and the conversion of the sPP lamellae into fibrils whose aspect ratio increases with further plastic deformation, respectively. The gel elastic properties can be understood quantitatively as those of a short fiber composite with a highly deformable matrix. At zero stress the random copolymer midblock chains that connect the fibrils cause these to make all angles to the tensile axis (low Einit), while at the maximum strain the stiff, crystalline sPP fibrils align with the tensile axis producing a strong, relatively stiff gel. The evolution of the

  15. Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

    PubMed Central

    De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

    2009-01-01

    The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

  16. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers

    SciTech Connect

    Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T.; Hillmyer, Marc A.

    2015-08-28

    Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.

  17. Temperature-Dependent Phase Behaviors in Cylinder-Forming Block Copolymers

    PubMed Central

    Ahn, Dae Up; Sancaktar, Erol

    2009-01-01

    We demonstrate that the temperature-dependent phase behaviors of parallel and perpendicular cylinder-forming block copolymers are governed by domain-domain segregation forces inherently present in block copolymer material itself. With increasing temperature, a parallel cylinder-forming block copolymer experienced a parallel cylinder straightening process before the order-disorder transition (ODT) and did not show long-range composition fluctuations near the ODT temperature due to the weak segregation forces between the block domains. A perpendicular cylinder-forming block copolymer with a strong segregation force between the block domains displayed cylinder orientation transition from perpendicular to parallel below the ODT temperature. On the other hand, a perpendicular cylinder-forming block copolymer material with an exceptionally strong segregation force between the block domains maintained its initial perpendicular cylinder orientation up to near the ODT temperature. In both cases of perpendicular cylinder-forming block copolymers, submicrometer-scale long-range composition fluctuations were observed well above the ODT temperature due to their intrinsically strong segregation forces between the block domains. PMID:19564947

  18. Anionic synthesis of block copolymers for photonics applications

    NASA Astrophysics Data System (ADS)

    Garces Cortes, Camila

    Anionic synthesis of well-defined polystyrene-block-polyvinylpyridine copolymers required the use of special conditions including lithium chloride and 1,1-diphenylethylene as additives, low temperature of reaction (-78°C), highly diluted monomer at -78°C and efficient stirring (Morton-type, creased reactor). Low molecular weight polystyrene-block-poly(2-vinylpyridine) copolymers (Mn = 6000 g/mol) were synthesized with average-molecular weights in agreement with the theoretically calculated Mns and narrow Mw/Mns (≤1.1). Polystyrene-block-polyvinylpyridine copolymers were selected for the fabrication of uniformly dispersed metal oxide nanoparticles (cobalt and iron oxides) due to the coordinating ligand character of the vinylpyridine units. The incorporation of the inorganic salts (1 mol-eq of inorg. salt per mol of vinylpyridine units) was 57 wt% when polystyrene- block-poly(2-vinylpyridine-co-4-vinylpyridine) (M n = 59,000 g/mol, Mw/Mn = 1.09, fv PVP = 0.19) was used and 18 wt% when polystyrene-block-poly(2-vinylpyridine) (Mn = 39,000 g/mol, Mw/Mn = 1.07, f v PVP = 0.14) was used. The end-capping reaction of polymeric chain-ends with 1,1-diphenylethylene (DPE) was studied using 2D NMR spectroscopic and MALDI-TOF mass spectrometric analyses. Oligomerization of DPE was observed using a 15-fold excess of DPE in the end-capping of poly(butadienyl)lithium (Mn = 2,200 g/mol, Mw/Mn = 1.06) but not in the case of poly(styryl)lithium (Mn = 2,000 g/mol, Mw/Mn = 1.02). Although oligomerization of DPE has been previously reported in the synthesis of 1,1-diphenylhexyllithium (6-11% oligomer with 5.4-fold excess of DPE), there are no studies showing the presence of DPE oligomer in the end-capping reaction of polymeric living carbanions. Additionally, the synthesis of poly(para-phenylene) has been studied using different precursor polymers [poly(1,3-cyclohexadienes) (Mn = 1,600 and 3,100 g/mol, Mw/Mn = 1.1 and 1.03) and poly(2-phenyl-1,3-cyclohexadiene) (Mn = 10,000 g/mol, Mw

  19. Diblock copolymers in bulk and in thin films: Morphology and kinetics

    NASA Astrophysics Data System (ADS)

    Podariu, Iulia Anca

    In this thesis I numerically study the phase diagram and kinetics of a diblock copolymers melt in both bulk and thin films in the strong segregation limit. I probe various values of the volume fraction, f, of the shorter block of the copolymer chains, spanning the bulk phase diagram for the diblock copolymers from a spherical body-centered cubic (BCC) phase to a hexagonally packed cylindrical (HCP) phase, to a bicontinuous gyroid phase (G), to finally a lamellar phase(L). Finite size and wetting properties of the substrate modify the film morphology by shifting the effective value of the composition in the film. For neutral substrates, the film morphology is shifted toward a smaller relative composition f, while for substrates which prefer the longer blocks of the copolymers, the film morphology is shifted toward a large value of f. A dramatic change in thin film morphology takes place for a small change in external parameters if one chooses the composition f to be at the borderline between two different bulk phases. The next question addressed is that of the control over the thin film structure in the case of a symmetric diblock copolymer films with a thickness smaller than the bulk equilibrium period. These films are cast on either flat or corrugated substrates. The results show that the formation of uniformly sized lateral domains that appear randomly on a flat surface can be controlled by using topographically patterned substrates. Control of lateral pattern fails if the distance between steps is smaller than the lamellar wavelength or the lateral size of the corrugation is larger than the bulk lamellar wavelength. For thin block copolymer (BCP) films on a homogeneous substrate, a fast domain growth exponent has recently been observed in experiments. I have carried out numerical simulations of ordering and domain growth in a two-dimensional system of BCP melts. The model calculations explicitly include viscous, hydrodynamic flow and provide a scaling

  20. Unexpected Consequences of Block Polydispersity on the Self-Assembly of ABA Triblock Copolymers

    SciTech Connect

    Widin, Joan M.; Schmitt, Adam K.; Schmitt, Andrew L.; Im, Kyuhyun; Mahanthappa, Mahesh K.

    2012-05-09

    Controlled/'living' polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use of these synthetic methods often introduces nontrivial molecular weight polydispersities, a type of chain length heterogeneity, into one or more of the copolymer blocks. While the self-assembly behavior of monodisperse AB diblock and ABA triblock copolymers is both experimentally and theoretically well understood, the effects of broadening the copolymer molecular weight distribution on block copolymer phase behavior are less well-explored. We report the melt-phase self-assembly behavior of SBS triblock copolymers (S = poly(styrene) and B = poly(1,4-butadiene)) comprised of a broad polydispersity B block (M{sub w}/M{sub n} = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M{sub w}/M{sub n} = 1.09-1.36), in order to identify the effects of chain length heterogeneity on block copolymer self-assembly. Based on synchrotron small-angle X-ray scattering and transmission electron microscopy analyses of seventeen SBS triblock copolymers with poly(1,4-butadiene) volume fractions 0.27 {le} f{sub B} {le} 0.82, we demonstrate that polydisperse SBS triblock copolymers self-assemble into periodic structures with unexpectedly enhanced stabilities that greatly exceed those of equivalent monodisperse copolymers. The unprecedented stabilities of these polydisperse microphase separated melts are discussed in the context of a complete morphology diagram for this system, which demonstrates that narrow dispersity copolymers are not required for periodic nanoscale assembly.

  1. Unexpected consequences of block polydispersity on the self-assembly of ABA triblock copolymers.

    PubMed

    Widin, Joan M; Schmitt, Adam K; Schmitt, Andrew L; Im, Kyuhyun; Mahanthappa, Mahesh K

    2012-02-29

    Controlled/"living" polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use of these synthetic methods often introduces nontrivial molecular weight polydispersities, a type of chain length heterogeneity, into one or more of the copolymer blocks. While the self-assembly behavior of monodisperse AB diblock and ABA triblock copolymers is both experimentally and theoretically well understood, the effects of broadening the copolymer molecular weight distribution on block copolymer phase behavior are less well-explored. We report the melt-phase self-assembly behavior of SBS triblock copolymers (S = poly(styrene) and B = poly(1,4-butadiene)) comprised of a broad polydispersity B block (M(w)/M(n) = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M(w)/M(n) = 1.09-1.36), in order to identify the effects of chain length heterogeneity on block copolymer self-assembly. Based on synchrotron small-angle X-ray scattering and transmission electron microscopy analyses of seventeen SBS triblock copolymers with poly(1,4-butadiene) volume fractions 0.27 ≤ f(B) ≤ 0.82, we demonstrate that polydisperse SBS triblock copolymers self-assemble into periodic structures with unexpectedly enhanced stabilities that greatly exceed those of equivalent monodisperse copolymers. The unprecedented stabilities of these polydisperse microphase separated melts are discussed in the context of a complete morphology diagram for this system, which demonstrates that narrow dispersity copolymers are not required for periodic nanoscale assembly. PMID:22280467

  2. Anisotropic Lithium Ion Conductivity in Single-Ion Diblock Copolymer Electrolyte Thin Films.

    PubMed

    Aissou, Karim; Mumtaz, Muhammad; Usluer, Özlem; Pécastaings, Gilles; Portale, Giuseppe; Fleury, Guillaume; Cloutet, Eric; Hadziioannou, Georges

    2016-02-01

    Well-defined single-ion diblock copolymers consisting of a Li-ion conductive poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PSLiTFSI) block associated with a glassy polystyrene (PS) block have been synthesized via reversible addition fragmentation chain transfer polymerization. Conductivity anisotropy ratio up to 1000 has been achieved from PS-b-PSLiTFSI thin films by comparing Li-ion conductivities of out-of-plane (aligned) and in-plane (antialigned) cylinder morphologies at 40 °C. Blending of PS-b-PSLiTFSI thin films with poly(ethylene oxide) homopolymer (hPEO) enables a substantial improvement of Li-ion transport within aligned cylindrical domains, since hPEO, preferentially located in PSLiTFSI domains, is an excellent lithium-solvating material. Results are also compared with unblended and blended PSLiTFSI homopolymer (hPSLiTFSI) homologues, which reveals that ionic conductivity is improved when thin films are nanostructured. PMID:26618916

  3. Evolution of homopolymer thin-film instability on surface-anchored diblock copolymers varying in composition.

    PubMed

    Cai, Xiao-Jing; Genzer, Jan; Spontak, Richard J

    2014-10-01

    The stability of molecularly thin polymer films deposited on various material substrates is of critical importance to many contemporary nanotechnologies involving functional coatings and nano/micropatterned surfaces, in which case the causes responsible for film destabilization must be fully understood. Previous experimental studies report that factors such as film thickness and polymer molecular weight play significant roles in governing the rate, as well as mechanism, of destabilization. Complementary theoretical predictions reveal that surface heterogeneities can likewise induce (and regulate the process of) destabilization. In this study, we investigate the destabilization rate and mechanism of homopolystyrene (PS) films differing in thickness on top of poly(styrene-b-methyl methacrylate) (SM) diblock copolymer monolayers varying in chemical composition anchored to flat silica-like substrates to examine the effect of surface constitution on PS stability. Copolymers with a long M block consistently promote PS dewetting by nucleation and growth, wherein the linear dewetting rate decreases monotonically with increasing PS molecular weight, film thickness, and S fraction in the SM copolymer. In analogous studies involving a copolymer with a relatively short M block, however, PS dewetting proceeds instead by spinodal dewetting that evolves gradually into nucleation and growth as the film thickness is increased. PMID:25259655

  4. How to Place Block Copolymer Molecules at the Interface of a Binary Blend

    NASA Astrophysics Data System (ADS)

    Chen, Zhong-Ren; Xu, Yuci; Zhong, Shuo

    2015-03-01

    Block copolymers have been used to reduce the domain size of immiscible polymer blends and thus improve the mechanical and other properties. The effectiveness of this method, however, depends on the percentage of these polymeric surfactants residing at the interface of the blend. In fact, theoretical as well as experimental work indicate that a large percentage of block copolymers form micelles in the bulk of one or both of the component polymers. These micelles may serve as weak spots initiating crack propagation. Previous work have been focused on the design of molecular architecture and synthesis of new block copolymers to address this problem. In this presentation, a simple mixing strategy is applied to make each block copolymer molecule stay at the interface. As one example, when this strategy is used to mix natural rubber (NR) with butadiene rubber (BR), a small amount of low molecular weight block copolymer (LIR) improves both processing characteristics such as melt viscosity and mechanical properties of cured samples, such as crack resistance. AFM micrographs show the much smaller domain size; and an original real-time monitoring system reveals the lowest crack growth rate. Using a model A/B/A-B binary blend, we have witnessed by microscopy that all block copolymer molecules form micelles at the first mixing step, and all of these micelles are disappeared and all block copolymer molecules stay at the interface after the second mixing step.

  5. Morphological Characteristics and Phase Behavior of Nanoparticle-Modified Block Copolymers

    NASA Astrophysics Data System (ADS)

    Bowman, Michelle; Bockstaller, Michael; Rasmussen, Kim; Samseth, Jon; Smith, Steven; Thompson, Russell; Spontak, Richard

    2007-03-01

    Block copolymers exhibit a wealth of nanoscale morphologies that continue to find use in a diverse variety of emergent (nano)technologies. While numerous studies have explored the effects of molecular confinement on such copolymers, few have examined the use of such objects to modify the morphological characteristics and phase behavior of microphase-ordered block copolymers. In this work, a poly(styrene-b-methyl methacrylate) (SM) diblock copolymer has been modified with surface-functionalized fumed silica (FS) and colloidal silica (CS). Dynamic rheological measurements have been conducted on the neat and nanoparticle-modified copolymer to generate a quantitative comparison with SM/FS and SM/CS nanocomposites. Transmission electron microscopy (TEM) and self-consistent field theory (SCFT) calculations have also been performed to further elucidate results obtained via dynamic rheology by establishing the morphological characteristics of the copolymer and the dispersion of the functionalized nanoparticles within the resultant nanocomposites.

  6. Effect of monomer sequencing on the phase behavior of novel block copolymer/homopolymer blends

    SciTech Connect

    Laurer, J.H.; Fung, J.C.; Agard, D.A.

    1996-12-31

    Blends consisting of a block copolymer and a parent or block-specific homopolymer exhibit macrophase or microphase separation, depending on (i) the homopolymer chain length relative to that of the host block, (ii) the bulk composition of the blend, and (iii) the state of the copolymer. Recent studies of copolymer/homopolymer blends composed of block, random or alternating copolymers have shown that monomer sequencing plays a crucial role in phase behavior and morphological development. In this work, we examine this effect more closely by probing local segment interactions in both the ordered and disordered block copolymer regimes. In the disordered regime, the effects of blend concentration and molecular weight disparity were analyzed using a poly[(styrene-r-isoprene){prime}-b-(styrene-r-isoprene){double_prime}] (S/I) {prime}-b-(S/I){double_prime} copolymer and three homopolystyrenes of varying molecular weight. To probe segmental interactions in the ordered regime, a series of poly[styrene-b-(styrene-r-isoprene)-b-isoprene] S(S/I)I triblock copolymers has been blended with a single low-molecular-weight homopolystyrene. The phase behavior of all these blends has been examined with transmission electron microscopy (TEM). Electron microtomography was also used to produce the first relatively high-resolution 3-D reconstruction of the L{sub 3} morphology in a copolymer-dilute blend.

  7. Bicontinuous ceramics with high surface area from block copolymer templates.

    PubMed

    Hsueh, Han-Yu; Ho, Rong-Ming

    2012-06-01

    Mesoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by hydrolysis of PLLA block. Well-defined polymer/ceramic nanohybrid materials with inorganic gyroid nanostructures in a PS matrix can be obtained by using the mesoporous PS as a template for sol-gel reaction. Titanium tetraisopropoxide (TTIP) is used as a precursor to give a model system for the fabrication of metal oxide nanostructures from reactive transition metal alkoxides. By controlling the rates of capillary-driven pore filling and sol-gel reaction, the templated synthesis can be well-developed. Also, by taking advantage of calcination, bicontinuous TiO(2) with controlled crystalline phase (i.e., anatase phase) can be fabricated after removal of the PS template and crystallization of TiO(2) by calcination leading to high photocatalytic efficiency. This new approach provides an easy way to fabricate high-surface-area and high-porosity ceramics with self-supporting structure and controlled crystalline phase for practical applications. As a result, a platform technology to fabricate precisely controlled polymer/ceramic nanohybrids and mesoporous ceramic materials can be established. PMID:22530553

  8. Flexible Battery Cathodes Enabled by Conductive Block Copolymers

    NASA Astrophysics Data System (ADS)

    Lutkenhaus, Jodie; Verduzco, Rafael; An, Hyosung; Lin, Yen-Hao; Lutkenhaus Laboratory Collaboration; Verduzco Laboratory Collaboration

    2015-03-01

    Alone, or as part of hybrid electrodes, conductive polymers are poised to play an integral role in the new and growing field of flexible or ``plastic'' power. Here we demonstrate that even small amounts of a poly(3-hexylthiophene)-block-poly(ethylene oxide) (P3HT-b-PEO) block copolymer, acting as an ion and electron conductor, can bring about significant improvements in energy storage and mechanical flexibility for V2O5 hybrid cathodes for Li-ion batteries. By following this approach, traditional inert polymer binders and carbon black additives are not needed. V2O5 alone has a high theoretical capacity that is limited in practical application by low conductivity. Further, V2O5 alone is brittle and breaks upon repeated flexure. P3HT-b-PEO serves to address both these issues. This presentation will cover how these hybrid electrodes are formed and the resulting physicochemical properties that lead to its enhanced flexibility and energy storage.

  9. Block-copolymer vesicles as nanoreactors for enzymatic reactions.

    PubMed

    Chen, Qi; Schönherr, Holger; Vancso, G Julius

    2009-06-01

    The impact of the spatial confinement of polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer (BCP) vesicles on the reactivity of encapsulated bovine pancreas trypsin is studied. Enzymes, as well as small molecules, are encapsulated with loading efficiencies up to 30% in BCP vesicles with variable internal volumes between 0.014 aL (internal vesicle diameter, d(in) = 30 nm) and 8 aL (d(in) = 250 nm), obtained by manipulating the vesicle preparation conditions. The kinetics of the trypsin-catalyzed reaction of a fluorogenic substrate inside and outside the vesicles is quantitatively estimated using fluorescence spectroscopic analyses in conjunction with the use of NaNO(2) as selective quencher for non-encapsulated fluorophores. The values of the catalytic turnover number obtained for reactions in differently sized nanoscale reactors show a significant increase (up to approximately 5x) with decreasing BCP vesicle volume, while the values of the Michaelis-Menten constant decrease. The observed increase in enzyme efficiency by two orders of magnitude compared to bulk solution is attributed to an enhanced rate of enzyme-substrate and molecule-wall collisions inside the nanosized reactors, as predicted in the literature on the basis of Monte Carlo simulations. PMID:19283796

  10. Surface Modification of Block Copolymer Through Sulfur Containing Plasma Treatment.

    PubMed

    Choi, Sang Wook; Shin, Jae Hee; Jeon, Min Hwan; Mun, Jeong Ho; Kim, Sang Ouk; Yeom, Geun Young; Kim, Kyong Nam

    2015-10-01

    Some of the important issues of block copolymer (BCP) as an application to the potential low cost next generation lithography are thermal stability and deformation during pattern transfer process in addition to defect density, line edge/width roughness, etc. In this study, sulfur containing plasma treatment was used to modify the BCP and the effects of the plasma on the properties of plasma treated BCP were investigated. The polystyrene hole pattern obtained from polystyrene polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) was initially degraded when the polystyrene hole was annealed at 190 °C for 15 min. However, when the hole pattern was treated using sulfur containing plasmas using H2S or SF6 up to 2 min, possibly due to the sulfurization of the polystyrene hole surface, no change in the hole pattern was observed after the annealing even though there is a slight change in hole shapes during the plasma treatment. The optimized plasma treated polystyrene pattern showed the superior characteristics as the mask layer by showing better thermal stability, higher chemical inertness, and higher etch selectivity during plasma etching. PMID:26726468

  11. Structure, Mechanics, and Transport in Block Copolymer-Nanoparticle Composites at the Macroscopic and Nanometer Lengthscales

    NASA Astrophysics Data System (ADS)

    Cheng, Vicki Alice

    2013-08-01

    Pluronic triblock copolymers self-assemble in water to form thermoreversible soft solids that comprise of periodically spaced micelles. The interstitial spacings of these micellar crystals are on the order of tens of nanometers, and have been used to template comparably sized nanoparticles with hydrodynamic diameters (Dh) ranging from 4-7 nm. Here, nanoparticle diffusivity is studied and modeled in these self-assembling block copolymers across a range of polymer concentrations. Transport in the disordered micellar solution is described as diffusion through a polymer solution, while diffusive behavior in the structured micellar phase is modeled as an activated hopping process. The effects of protein loading, shear alignment, particle type, and block copolymer composition on particle transport are also examined, and they affect particle diffusivity to varying degrees. Block copolymer architecture influences the micellar structure and dimensions, which in turn affects protein templating and protein aggregation behavior. The overall micellar dimensions are smaller in block copolymers with shorter block lengths, and efforts to template particles which are larger than the interstitial spacings result in changes to the block copolymer structure and mechanics. It is possible, however, for block copolymers to accommodate a limited amount of particles which are larger than the estimated micellar interstitial site. When examining protein aggregation behavior in block copolymers with varying PEO chain lengths, striking differences in aggregation behavior are observed as well. Ultimately, this work underscores the interplay between the structure, mechanics, and transport behavior in nanoparticle-block copolymer composites, and this knowledge can be applied towards the design of self-assembling nanoscale materials.

  12. Confinement effects on the miscibility of block copolymer blends.

    PubMed

    Spencer, Russell K W; Matsen, Mark W

    2016-04-01

    Thin films of long and short symmetric AB diblock copolymers are examined using self-consistent field theory (SCFT). We focus on hard confining walls with a preference for the A component, such that the lamellar domains orient parallel to the film with an even number ν of monolayers. For neat melts, confinement causes the lamellar period, D, to deviate from its bulk value, Db, in order to be commensurate with the film thickness, i.e., L = νD/2. For blends, however, the melt also has the option of macrophase separating into ν(l) large and ν((s)) small monolayers so as to provide a better fit, where L = ν(l)D(l)/2 + ν(s)D((s))/2. In addition to performing full SCFT calculations of the entire film, we develop a semi-analytical calculation for the coexistence of thick and thin monolayers that helps explain the complicated interplay between miscibility and commensurability. PMID:27106106

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

    NASA Astrophysics Data System (ADS)

    Bowman, Michelle Kathleen

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

  14. Patterns with PS-b-PMMA block copolymer on various substrates and their applications

    NASA Astrophysics Data System (ADS)

    Alam, Md. Mahbub; Lee, Yu-Rim; Jung, Woo-Gwang

    2011-01-01

    High density arrays of nanostructures over large area can be formed by self-assembly of block copolymers on a variety of substrates such as silica deposited silicon wafer, glass, GaN, PET etc. This block copolymer thin film, such that the domains are oriented perpendicularly to the substrate, is particularly useful for the formation of templates for patterns. The degradation and elimination of the minor component transforms the material into an array of nanopores to form some patterned template that offer potential benefits in a number of applications. The morphology of the polymer surface is strongly dependent on the thickness of the polymer layer. Moreover it is necessary to control the size and shape in order to get the desired properties. Spin coating fallowed by baking the polymer solution onto the substrate self assembles the components of the polymer. PS and PMMA have significantly different photodegradation properties. Exposure to ultraviolet radiation degrades the PMMA (polymethyl methacrylate) chain that can be removed by rinsing in acetic acid giving patterned holes. Sonicating the samples in different solutions in different steps gives fingerprint pattern or sometimes patterns with PS cylindrical domains with large interstitial spaces. Moreover the interstitial space depends on the composition of the polymer solution. All these controlled patterns made on GaN, Glass can be applied to make photonic crystal

  15. High Aspect Ratio Sub-15 nm Silicon Trenches From Block Copolymer Templates

    NASA Astrophysics Data System (ADS)

    Gu, Xiaodan; Liu, Zuwei; Gunkel, Ilja; Olynick, Deirdre; Russell, Thomas; University of Massachusetts Amherst Collaboration; Oxford Instrument Collaboration; Lawrence Berkeley National Lab Collaboration

    2013-03-01

    High-aspect-ratio sub-15 nm silicon trenches are fabricated directly from plasma etching of a block copolymer (BCP) mask. Polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) 40k-b-18k was spin coated and solvent annealed to form cylindrical structures parallel to the silicon substrate. The BCP thin film was reconstructed by immersion in ethanol and then subjected to an oxygen and argon reactive ion etching to fabricate the polymer mask. A low temperature ion coupled plasma with sulfur hexafluoride and oxygen was used to pattern transfer block copolymer structure to silicon with high selectivity (8:1) and fidelity. The silicon pattern was characterized by scanning electron microscopy and grazing incidence x-ray scattering. We also demonstrated fabrication of silicon nano-holes using polystyrene-b-polyethylene oxide (PS-b-PEO) using same methodology described above for PS-b-P2VP. Finally, we show such silicon nano-strucutre serves as excellent nano-imprint master template to pattern various functional materials like poly 3-hexylthiophene (P3HT).

  16. Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends

    SciTech Connect

    Liedel, Clemens; Schindler, Kerstin; Pavan, Mariela J.; Lewin, Christian; Pester, Christian W; Ruppel, Markus A; Urban, Volker S; Shenhar, Roy; Boker, Alexander

    2013-01-01

    External electric fi elds readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-fi eld-induced alignment of a lamellae-forming polystyrene- block -poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-fi eldassisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such fi lms under benign experimental conditions.

  17. Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

    DOEpatents

    Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

    2010-05-18

    The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

  18. Bottlebrush Copolymer Morphology Transition: Influence of Side Chain Length and Block Volume Fraction

    NASA Astrophysics Data System (ADS)

    Gai, Yue; Song, Dong-Po; Watkins, James

    Brush block copolymers synthesized via living ring-opening metathesis polymerization (ROMP) offer unique advantages as templates for functional hybrid materials. Unlike linear block copolymer, the bottlebrush polymer phase transition not only depends on volume fractions of the two blocks but also on side chain length. Here we report the morphology transitions of PS-b-PEO bottlebrush copolymer (BBCP) as a function of PEO side chain length and block volume fraction. For the BBCPs with similar side chain lengths, highly ordered lamellar morphologies were observed with PEO volume fractions in a wide range from 32 vol% to 72 vol%, which is significantly different from that of traditional linear block copolymers. This study will lay the groundwork for nanostructure fabrications using the BBCPs and provides new insights into the phase behavior of the new type of materials. This work was supported by NSF center for Hierarchical Manufacturing at the University of Massachusetts, Amherst.

  19. A strategy to explore stable and metastable ordered phases of block copolymers.

    PubMed

    Xu, Weiquan; Jiang, Kai; Zhang, Pingwen; Shi, An-Chang

    2013-05-01

    Block copolymers with their rich phase behavior and ordering transitions have become a paradigm for the study of structured soft materials. A major challenge in the study of the phase behavior of block copolymers is to obtain different stable and metastable phases of the system. A strategy to discover complex ordered phases of block copolymers within the self-consistent field theory framework is developed by a combination of fast algorithms and novel initialization procedures. This strategy allows the generation of a large number of candidate structures, which can then be used to construct phase diagrams. Application of the strategy is illustrated using ABC star triblock copolymers as an example. A large number of candidate structures, including many three-dimensionally ordered phases, of the system are obtained and categorized. A phase diagram is constructed for symmetrically interacting ABC star triblock copolymers. PMID:23551204

  20. Efficacy of Different Block Copolymers in Facilitating Microemulsion Phases in Polymer Blend Systems

    NASA Astrophysics Data System (ADS)

    Pandav, Gunja; Ganesan, Venkat

    2014-03-01

    Polymeric microemulsions are formed in a narrow range of phase diagram when a blend of immiscible homopolymers is compatibilized by copolymers. In this study, we consider the ternary blend system of A and B homopolymers mixed with block copolymers containing A and B segments, and probe the efficacy of different copolymer configurations in promoting the formation of microemulsion phases. Specifically, we consider: (a) Monodisperse diblock copolymers; (b) Diblock copolymers with bidisperse molecular weights (MW); (c) Block copolymers having MW polydispersity in one of the blocks; (d) Diblock copolymers having monodisperse MW but bidispersity in average composition; and (e) Gradient copolymers exhibiting a linear variation in the average composition. Using single chain in mean field simulations effected in two dimensions, we probe the onset of formation and the width of the bicontinuous microemulsion channel in the ternary phase diagram of homopolymer blended with compatibilizer. We rationalize our results by explicitly quantifying the interfacial activity and the influence of fluctuation effects in the respective copolymer systems.

  1. Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

    SciTech Connect

    Michael Duane Determan

    2005-12-17

    The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi

  2. Synthesis and Characterization of Poly(3-alkylthiophene)-containing Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ho, Victor

    temperatures can be used to directly manipulate, and thereby balance, the competition between the driving forces for crystallization and self-assembly. As evidence, the nanoscale structure is shown to be directly controlled via synthesis of block copolymers in which one block is the low melting temperature semiconducting polymer, poly(3-(2-ethylhexyl)thiophene). A wide range of morphologies with curved interfaces are observed which, in the past, have been precluded by the crystallization of poly(3-alkylthiophenes) with unbranched aliphatic side chains such as poly(3-hexylthiophene). Importantly, confinement of the conjugated polymer to nanoscale domains is not detrimental to the crystallinity or to charge transport over device-scale dimensions. Additionally, this approach is shown to be effective for a number of different chemistries providing a flexible methodology for obtaining periodic, semiconducting domains on the nanoscale. Together, these simple synthetic strategies can be used to tune the morphology of various length scales of thin film active layers and provide synthetic rules for design of novel semiconducting polymer systems.

  3. Perpendicular Orientation of Nanodomains on Versatile Substrates through Self-Neutralization Induced by Star-Shaped Block Copolymers

    NASA Astrophysics Data System (ADS)

    Kim, Mooseong; Jang, Sangshin; Lee, Kyu Seong; Moon, Hong Chul; Kwak, Jongheon; Park, Jicheol; Jeon, Gumhye; Kim, Jin Kon

    A novel self-neutralization concept is introduced by designing molecular architecture of a block copolymer. Star-shaped 18 arm poly(methyl methacrylate)-block-polystyrene copolymers ((PMMA-b-PS)18) exhibiting lamellar and PMMA cylindrical nanodomains are synthesized. When a thin film of (PMMA-b-PS)18 is spin-coated on a substrate, vertically aligned lamellar and cylindrical nanodomains are obtained without any pre- or post-treatment, although thermal annealing for a short time (less than 30 min) is required to improve the spatial array of vertically aligned nanodomains. This result is attributed to the star-shaped molecular architecture that overcomes the difference in the surface affinity between PS and PMMA chains. Moreover, vertical orientations are observed on versatile substrates, for instance, semiconductor (Si, SiOx), metal (Au), PS or PMMA-brushed substrate, and a flexible polymer sheet of polyethylene naphthalate.

  4. On the Use of Self-Assembling Block Copolymers to Toughen A Model Epoxy

    NASA Astrophysics Data System (ADS)

    Chen, Yilin

    Block copolymers have been receiving considerable attention in toughening epoxy due to their ability to form a wide variety of nanostructures. This study focuses on using both triblock and diblock copolymers to improve the fracture toughness of an aromatic-amine cured epoxy system. The curing system consisted of 1,3- phenylenediamine (mPDA) as curing agent and aniline as a chain extender. Three triblock copolymers and three diblock copolymers were incorporated in the same lightly crosslinked model epoxy system, which was chosen to mimic an underfill material in flip-chip packaging for the microelectronics industry. In this research, rubber particles were formed in situ using self-assembling block copolymers. Mechanical, thermal and microscopic studies were conducted with the main goal to study the relationship between the block parameters and the final morphologies and their effects on static and dynamic mechanical properties of the toughened resin, especially fracture toughness. In these block-copolymer-modified epoxies, spherical micelles and wormlike micelles were obtained by varying block lengths, molecular weight, polarities and compositions. It was found that miscibility of the epoxy-miscible block played a crucial role in the formation of different types of morphologies. At a low loading level, diblock copolymers were able to toughen the model epoxy as effectively as triblock copolymers. The fracture toughness was improved to almost three times with respect to that of the neat resin with addition of 10 phr AM*-27. At the same time, other mechanical properties, such as yield strength and modulus, were well retained. Incorporation of block copolymers did not have a significant effect on glass transition temperature but caused an increase in coefficient of thermal expansion (CTE) of the modified epoxy. Particle cavitation and matrix void growth were proved to be the toughening mechanisms for SBM-Modified epoxies. However, these typical toughening mechanisms for

  5. Fluorosilicone multi-block copolymers tethering quaternary ammonium salt groups for antimicrobial purpose

    NASA Astrophysics Data System (ADS)

    Zhou, Fang; Qin, Xiaoshuai; Li, Yancai; Ren, Lixia; Zhao, Yunhui; Yuan, Xiaoyan

    2015-08-01

    Symmetrically structured fluorosilicone multi-block copolymers containing poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(hexafluorobutyl methacrylate) (PHFBMA) were sequentially synthesized via reversible addition-fragmentation chain transfer polymerization, using a polydimethylsiloxane (PDMS) chain transfer agent with dithiocarbonate groups at both ends. Then, the CBABC-type block copolymers were quaternized with n-octyliodide to tether quaternary ammonium salt (QAS) groups in the PDMAEMA blocks for the antimicrobial use. The obtained fluorosilicone copolymers showed clear variations in the C-N+ composition and surface morphology on their films depending on the content of the PHFBMA blocks, which were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The results indicated that the symmetrical CBABC structure favored PDMS and QAS tethered blocks migrating to the film surface. With the mass percentage of the PHFBMA increased from 0 to 32.5%, the surface roughness of the copolymer film decreased gradually with a tendency to form a smooth surface. Owing to the surface properties, fluorosilicone multi-block copolymers containing a certain amount of PHFBMA with higher C-N+ content and relatively smooth morphology demonstrated obvious antimicrobial activity against Gram-positive bacteria, Bacillus subtilis and Gram-negative bacteria, Escherichia coli. The functionalized multi-block copolymers based on fluorosilicone and QAS groups would have potential applications in antimicrobial coatings.

  6. Theoretical and Experimental Investigations of Contact Hole Shrink using PS-PMMA Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ginzburg, Valeriy; Hustad, Phillip; Weinhold, Jeffrey; Sharma, Rahul; Chuang, Vivian; Trefonas, Peter

    2012-02-01

    One possible application of block copolymer directed self-assembly (DSA) involves rectification or ``shrink'' of contact holes in a polarity switched photoresist (see, e.g., J. Cheng et al., ACS Nano 8, 4815 [2010]). The block copolymer (e.g., PS-PMMA) undergoes ordering inside the cylindrical hole; the central (PMMA) domain is then etched out so that the hole diameter is effectively reduced. We utilize strong segregation theory (SST) and numerical self-consistent field theory (SCFT) to calculate the phase behavior of the block copolymers as function of their molecular weight and composition, as well as the contact hole diameter and the surface chemistry of the walls. The model predictions were compared with experimental data, and a good agreement was found. The results illustrate how modeling can serve to guide block copolymer selection for DSA contact hole rectification application.

  7. Mussel-inspired block copolymer lithography for low surface energy materials of teflon, graphene, and gold.

    PubMed

    Kim, Bong Hoon; Lee, Duck Hyun; Kim, Ju Young; Shin, Dong Ok; Jeong, Hu Young; Hong, Seonki; Yun, Je Moon; Koo, Chong Min; Lee, Haeshin; Kim, Sang Ouk

    2011-12-15

    Mussel-inspired interfacial engineering is synergistically integrated with block copolymer (BCP) lithography for the surface nanopatterning of low surface energy substrate materials, including, Teflon, graphene, and gold. The image shows the Teflon nanowires and their excellent superhydrophobicity. PMID:22021119

  8. Phase Behavior of Star-shaped polystyrene-block-poly(methyl methacrylate) Copolymers

    NASA Astrophysics Data System (ADS)

    Jang, Sangshin; Moon, Hongchul; Lee, Youngmin; Kim, Jin Kon

    2012-02-01

    Star-shaped polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) was synthesized by utilizing α-cyclodextrin (α-CD) as a junction point of the star-shaped block copolymer. Eighteen hydroxyl groups on α-CD were substituted with bromine by the reaction with α-bromoisobutyryl bromide for atom transfer radical polymerization. We found that the number of bromine substituted arms per one α-CD was higher than 16 measured by nuclear magnetic resonance and Matrix-assisted laser desorption/ionization. We could control molecular weight of this unusual kind of block copolymer depending on polymerization times. Those polymers were characterized by gel permeation chromatography and nuclear magnetic resonance. Phase behavior of these star-shaped block copolymers were investigated.

  9. Surface Dynamics of Block Copolymer Films by X-ray Photon Correlation Spectroscopy

    SciTech Connect

    Song, Sanghoon; Cha, Wonsuk; Lee, Heeju; Li, Xiaolong; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh; Ruehm, Adrian; Sinha, S. K.

    2009-04-19

    We investigated the structure and dynamics of supported block copolymer films of poly(styrene)-b-poly(dimethylsiloxane)(PS-b-PDMS) in the spherical phase by x-ray photon correlation spectroscopy (XPCS) in grazing angle geometry. The temperature range studied was between 160 deg. and 210 deg. C, much higher than glass transition temperature (Tg), with thickness from 40 nm to 600 nm. Using x-ray reflectivity and x-ray photoelectron spectroscopy (XPS), we found that the PDMS-rich layer near the surface appeared at a temperature higher than Tg. Universal scaling of the dynamics, even with the bilayer model, was observed. From the fitting with the bilayer model, viscosities from both layers were obtained. The results from the surface dynamics are compared with the theory of overdamped thermal capillary waves on thin films.

  10. Nanostructured Colloidal Particles by Confined Self-Assembly of Block Copolymers in Evaporative Droplets

    NASA Astrophysics Data System (ADS)

    Kim, Minsoo; Yi, Gi-Ra

    2015-06-01

    Block copolymers (BCPs) can create various morphology by self-assembly in bulk or film. Recently, using BCPs in confined geometries such as thin film (one-dimension), cylindrical template (two-dimension), or emulsion droplet (three-dimension), nanostructured BCP particles have been prepared, in which unique nanostructures of the BCP are formed via solvent annealing process and can be controlled depending on molecular weight ratio and interaction parameter of the BCPs, and droplet size. Moreover, by tuning interfacial property of the BCP particles, anisotropic particles with unique nanostructures have been prepared. Furthermore, for practical application such as drug delivery system, sensor, self-healing, metamaterial, and optoelectronic device, functional nanoparticles can be incorporated inside BCP particles. In this article, we summarize recent progress on the production of structured BCP particles and composite particles with metallic nanoparticles.

  11. Hierarchical Self-Assembled Structures from POSS-Containing Block Copolymers Synthesized by Living Anionic Polymerization

    SciTech Connect

    Hirai, Tomoyasu; Leolukman, Melvina; Jin, Sangwoo; Goseki, Raita; Ishida, Yoshihito; Kakimoto, Masa-aki; Hayakawa, Teruaki; Ree, Moonhor; Gopalan, Padma

    2010-03-16

    Two kinds of polyhedral oligomeric silsesquioxane (POSS)-containing block copolymers (BCPs), namely PS-b-PMAPOSS and PMMA-b-PMAPOSS, were synthesized by living anionic polymerization. A wide range of molecular weights were obtained with a very narrow polydispersity index of less than 1.09. The bulk samples prepared by slow evaporation from a polymer solution in chloroform exhibit well-defined microphase-separated structures with long-range order. Thermal annealing induced hierarchical structures consisting of a smaller length scale ordered crystalline POSS domains within the larger microphase-separated structures. We report detailed structural characterization of these hierarchical structures in bulk and thin films by transmission electron microscopy and grazing incidence wide-angle X-ray scattering (GIWAXS). On the basis of this structural analysis, we propose a model for the formation of an orthorhombic lattice structure through the aggregation of POSS segments which formed a helix-like structure.

  12. Multilayer block copolymer meshes by orthogonal self-assembly

    PubMed Central

    Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R.; Alexander-Katz, Alfredo; Ross, Caroline A.; Berggren, Karl K.

    2016-01-01

    Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders. PMID:26796218

  13. Two-Dimensional Confinement of Nanorods in Block Copolymer Domains

    NASA Astrophysics Data System (ADS)

    Liu, Yu; Deshmukh, Ranjan; Composto, Russell

    2008-03-01

    To control their unique electrical and optical properties, one-dimensional metallic/semiconductor nanoparticles need to be aligned and assembled within a host material. In our research, we investigated the assembly of gold nanorods (NRs) in films of a symmetric diblock copolymer, poly(styrene-b-methyl methacrylate), PS-b-PMMA (211kg/mol). The NR length and diameter was 42nm and 13nm, respectively. The NRs were grafted with a short PEG-brush (5kg/mol). During solvent annealing, the NRs become oriented as the PS-b-PMMA chains assemble into a parallel lamellar morphology. The NRs are selectively sequestered and confined in the PMMA domains, which are narrower than the NR length, due to the favorable interaction between the PEG brush and PMMA block. This confinement orients 71% of NRs within ± 5^o of the lamella plane. This route to produce alternating layers containing conducting NRs separated by dielectric domains has the potential for fabricating self-assembled nanodevices. The thermal stability of the NRs in PS-b-PMMA and homo PMMA films will also be discussed.

  14. Multilayer block copolymer meshes by orthogonal self-assembly

    NASA Astrophysics Data System (ADS)

    Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R.; Alexander-Katz, Alfredo; Ross, Caroline A.; Berggren, Karl K.

    2016-01-01

    Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders.

  15. Non-crosslinked, amorphous, block copolymer electrolyte for batteries

    DOEpatents

    Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

    2006-04-11

    Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

  16. The packing of soft materials: Molecular asymmetry, geometric frustration and optimal lattices in block copolymer melts

    NASA Astrophysics Data System (ADS)

    Grason, Gregory M.

    Melts of block copolymers provide an ideal route to engineering well-controlled structures on nanometer length scales. Through the control of only a few thermodynamic parameters, these systems can be tuned to self-assemble into periodic structures of an astounding variety. It is known that geometry plays a particularly important role in determining equilibrium structure since phase behavior of copolymer melts is generically insensitive to detail at the monomeric scale. Here, we explore a particular way in which the geometry of packing objects in three dimensions frustrates the internal configurations of segregated block copolymer domains. In particular, we find that lattices of spherical micelles are sensitive to the periodic structure of the lattice arrangement because these micelles are forced to occupy the non-ideal, polyhedral unit cells of the lattice. By analyzing the energetics of block copolymer melts in the limit of strongly-segregated domains, we find that the interfaces which separate unlike polymer domains tend to adopt the polyhedral shape of the lattice unit cell, and this tendency is entirely controlled by the specific copolymer architecture. Furthermore, in the limit where interfaces are perfectly polyhedral, a remarkable simplicity emerges, and the relative stability of competing lattice arrangements of micelles can be assessed purely in terms of geometric measures of the two-dimensional lattice unit cell. From this analysis we predict the stability of a novel cubic arrangement spherical micelles in block copolymer melts, the A15 lattice. To corroborate our geometric arguments we develop and implement a numerical self-consistent field theory for melts of highly asymmetric block copolymers. This field theory allows us to systematically and efficiently explore the equilibrium phase behavior of asymmetric copolymer melts as a function of molecular architecture. These numerical results bear out the predictions of our geometric analysis and confirm that

  17. Directed assembly of supramolecular copolymers in thin films

    NASA Astrophysics Data System (ADS)

    Muller, Marcus; Daoulas, Kostas Ch.; Cavallo, Anna; Shenhar, Roy

    2011-03-01

    Using computer simulation of a coarse-grained model for supramolecular polymers we investigate the potential of quasi-block copolymers (QBCP) assembled on chemically patterned substrates for creating device-oriented nanostructures. QBCP are comprised of AB diblock copolymers and supramolecular B segments that can reversibly bond to any available B terminus, either on the copolymers or the B oligomers, creating a polydisperse blend of B homopolymers, AB and ABA copolymers. We focus on an AB incompatibility, χ , and strength of supramolecular bonds where a lamellar morphology, a bicontinous structure and a macrophase-separated state have comparable free energy in the bulk. We consider substrate patterns with perpendicularly crossing, A-preferential lines and demonstrate their defect-free replication by QBCP. The same QBCP replicates simultaneously patterns differing by up to 50 % in their length scales, illustrating the high versatility of QBCP materials. We discuss the interplay between pattern geometry and distribution of molecular architectures and verify the key role of supramolecular associations for replicating patterns with different length scales.

  18. Tailored Assemblies of Rod-Coil Poly(3-hexylthiophene)-b-Polystyrene Diblock Copolymers: Adaptable Building Blocks for High-Performance Organic Field-Effect Transistors

    SciTech Connect

    Xiao, Kai; Yu, Xiang; Chen, Jihua; Lavrik, Nickolay V; Hong, Kunlun; Sumpter, Bobby; Geohegan, David B

    2011-01-01

    The self-assembly process and resulting structure of a series of conductive diblock copolymer thin films of Poly(3-hexylthiophene)-b-Polystyrene (P3HT-b-PS) have been studied by TEM, SAED, GIXD and AFM and additionally by first principles modeling and simulation. By varying the molecular weight of the P3HT segment, these block copolymers undergo microphase separation and self-assemble into nanostructured sphere, lamellae, nanofiber, and nanoribbon in the films. Within the diblock copolymer thin film, the convalently bonded PS blocks segregated to form amorphous domains, however, the conductive P3HT blocks were crystalline, exhibiting highly-ordered molecular packing with their alkyl side chains aligned along to the normal to the substrate and the - stacking direction of the thiophene rings aligned parallel to the substrate. The conductive P3HY block copolymers exhibited significant improvements in organic feild-effect transistor (OFET) performance and environmental stability as compared to P3HT homopolymers, with up to a factor of two increase in measured moblity (0.08 cm2/Vs ) for the P4 (85 wt% P3HT). Overall, this work demonstrates that the high degree of molecular order induced by bock copolymer phase separation can improve the transport properties and stability of conductive polymer critical for high-performance OFET s.

  19. Effects of Sequence Distribution, Concentration and pH on Gradient and Block Copolymer Micelle Formation in Solution

    NASA Astrophysics Data System (ADS)

    Marrou, Stephen; Kim, Jungki; Wong, Christopher; Torkelson, John

    2011-03-01

    Gradient copolymers are a relatively new class of materials with a gradual change in comonomer composition along the copolymer chain length, which have exhibited unique material properties in comparison to random and block copolymers. Here we extend this architecture to amphiphilic systems that form micelles in solvent, as the effect of a nonuniform comonomer sequence distribution is expected to strongly influence critical aggregation phenomena. Utilizing pyrene as a fluorescence probe, we determined that gradient copolymers present an intermediate critical aggregation concentration in comparison to analogous block and random copolymers. The effect of gradient architecture on a pH-sensitive copolymer was also investigated, concluding that gradient sequencing significantly impacts the solubility and critical aggregation pH when compared to block and random copolymers of similar composition, providing further evidence that gradient architectures introduce a powerful means of tuning properties between block and random copolymers.

  20. Mechano-responsive hydrogels crosslinked by reactive block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Xiao, Longxi

    Hydrogels are crosslinked polymeric networks that can swell in water without dissolution. Owing to their structural similarity to the native extracelluar matrices, hydrogels have been widely used in biomedical applications. Synthetic hydrogels have been designed to respond to various stimuli, but mechanical signals have not incorporated into hydrogel matrices. Because most tissues in the body are subjected to various types of mechanical forces, and cells within these tissues have sophisticated mechano-transduction machinery, this thesis is focused on developing hydrogel materials with built-in mechano-sensing mechanisms for use as tissue engineering scaffolds or drug release devices. Self-assembled block copolymer micelles (BCMs) with reactive handles were employed as the nanoscopic crosslinkers for the construction of covalently crosslinked networks. BCMs were assembled from amphiphilic diblock copolymers of poly(n-butyl acrylate) and poly(acrylic acid) partially modified with acrylate. Radical polymerization of acrylamide in the presence of micellar crosslinkers gave rise to elastomeric hydrogels whose mechanical properties can be tuned by varying the BCM composition and concentration. TEM imaging revealed that the covalently integrated BCMs underwent strain-dependent reversible deformation. A model hydrophobic drug, pyrene, loaded into the core of BCMs prior to the hydrogel formation, was dynamically released in response to externally applied mechanical forces, through force-induced reversible micelle deformation and the penetration of water molecules into the micelle core. The mechano-responsive hydrogel has been studied for tissue repair and regeneration purposes. Glycidyl methacrylate (GMA)-modified hyaluronic acid (HA) was photochemically crosslinked in the presence of dexamethasone (DEX)-loaded crosslinkable BCMs. The resultant HA gels (HAxBCM) contain covalently integrated micellar compartments with DEX being sequestered in the hydrophobic core. Compared

  1. Electrically conductive doped block copolymer of polyacetylene and polyisoprene. [Soluble in organic solvents

    DOEpatents

    Aldissi, M.

    1984-06-27

    An electrically conductive block copolymer of polyisoprene and polyacetylene and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I/sub 2/ to give it an electrical conductivity in the metallic regime.

  2. Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

    DOE PAGESBeta

    Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; Smith, Gregory Scott; Do, Changwoo

    2015-05-15

    The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well asmore » by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.« less

  3. Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

    SciTech Connect

    Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; Smith, Gregory Scott; Do, Changwoo

    2015-05-15

    The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well as by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.

  4. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups.

    PubMed

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b-poly(3,3-bis(Hydroxymethyl-triazolylmethyl) oxetane)-b-polylactide (PLA-b-PHMTYO-b-PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b-poly(3,3-Diazidomethyloxetane)-b-polylactide (PLA-b-PBAMO-b-PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following "Click" reaction of PLA-b-PBAMO-b-PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b-PHMTYO-b-PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b-PHMTYO-b-PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10(-4)mg/mL and 3.9 × 10(-5)mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b-PHMTYO-b-PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. PMID:25175206

  5. Plasmonic nanostructures based on block copolymer templates for efficient organic solar cells

    NASA Astrophysics Data System (ADS)

    Go, Seung Jae; Lee, Dong-Eun; Lee, Dong Hyun; Chin, Byung Doo

    2016-01-01

    Plasmonic nanostructures fabricated from self-assembled patterns of block copolymers (BCPs) were applied for organic solar cells (OSCs). A thin film of a cylinder-forming polystrene- block-poly(2-vinylpyridine) copolymer (PS- b-P2VP) was spin-coated on the transparent electrode of the OSCs, where nanostructures such as dot, dot with mixed line, and line patterns emerged during different solvent annealing processes. Selective conversion of hydrogen tetrachloroaurate (III) (HAuCl4) in P2VP blocks yielded gold (Au) nanostructures, which were used to trigger the localized surface plasmonic resonance (LSPR) effect at the OSCs. Plasmonic nanostructures with almost similar scales of BCP patterns were formed at the anode/buffer interface at the OSC, showing no-table enhancements of the short circuit current ( J sc) and the power conversion efficiency (3.57% for the reference compared to 4.35% for the optimum LSPR-OSC) as the size and the anisotropy of Au patterns changed from a simple dot through an integrated dot-line pattern to a line pattern. Based on the experimental analyses of the light absorption, photoluminescence, and exciton lifetime of OSC, such an enhancement would be mainly attributed to size-dependent LSPR-induced scattering and absorption at the OSC's active layer, which is not in intimate contact with the Au nanostructures. Up to a 26% increase in the power conversion efficiency could be observed at the plasmonic structures from BCP template, providing an accurately tuning and powerful tailoring of the LSPR-enhancing patterns for the OSCs.

  6. Fluorine effects on morphology and surface energy of diblock copolymer thin films

    NASA Astrophysics Data System (ADS)

    Shrestha, Umesh; Perahia, Dvora; Clarson, Stephen

    2015-03-01

    The interfacial composition and structure formed by the segregation between the incompatible blocks in a diblock copolymer thin film influence the stability and response of the film to external stimuli. Introduction of fluorine enhances the interfacial energy as well as chemical and thermal stability of the polymer film. Here we follow the interfacial structure and response of Si containing diblock co-polymer polytrifluoro propyl methyl siloxane-polystyrene (PTEPMS-PS) with the SiF fraction ranging from 0.03 to 0.5 in surface of the films as a function of temperature and solvent, using atomic force microscopy and contact angle measurement. We found that the tendency of the fluorine to migrate towards surface affects the surface energy while Si in backbone enhances the flexibility of the chains. Thin films prepared from selective good solvent for one of the blocks and good solvent for both blocks formed different structures compared to their melts. Correlation between morphology and volume fraction is dominant above the Tg of the polystyrene whereas below Tg limited effect is observed. NSF DMR 0907390.

  7. Synthesis of carboxylic block copolymers via reversible addition fragmentation transfer polymerization for tooth erosion prevention.

    PubMed

    Lei, Y; Wang, T; Mitchell, J W; Qiu, J; Kilpatrick-Liverman, L

    2014-12-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and (1)H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet-visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

  8. Synthesis of Carboxylic Block Copolymers via Reversible Addition Fragmentation Transfer Polymerization for Tooth Erosion Prevention

    PubMed Central

    Lei, Y.; Wang, T.; Mitchell, J.W.; Qiu, J.; Kilpatrick-Liverman, L.

    2014-01-01

    Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and 1H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet–visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

  9. Double network physical gels from elastin-like polypeptide block copolymers: nanoscale control of thermoresponsive reinforcement

    NASA Astrophysics Data System (ADS)

    Glassman, Matthew; Olsen, Bradley

    2014-03-01

    Triblock copolymers with associative protein midblocks and thermoresponsive endblocks form shear thinning hydrogels with a low yield stress at low temperatures, but can be reinforced by a self-assembled network of the endblock aggregates. Here, we compare the use of bioengineered elastin-like polypeptides (ELPs) to synthetic poly(N-isopropylacrylamide) (PNIPAM) as endblocks to control the self-assembly of the reinforcing network. The temperature dependence of the mechanics of these hydrogels is a strong function of the domain size and morphology in the endblock network. Despite the architectural similarities, triblock ELP fusions and PNIPAM bioconjugates exhibit distinct reinforcement maxima at fixed block composition and polymer concentration, and these differences can be attributed to the nanostructural features of the two systems. Furthermore, in ELP fusions, the amino acid sequence can be readily modified to manipulate the solvation kinetics of the endblock domains. Finally, various endblocks have been combined to form triblock terpolymer hydrogels, demonstrating how the choice of thermoresponsive blocks can be used to tune the reinforcement of shear thinning hydrogels.

  10. Perpendicularly oriented sub-10-nm block copolymer lamellae by atmospheric thermal annealing for one minute

    NASA Astrophysics Data System (ADS)

    Seshimo, Takehiro; Maeda, Rina; Odashima, Rin; Takenaka, Yutaka; Kawana, Daisuke; Ohmori, Katsumi; Hayakawa, Teruaki

    2016-01-01

    The directed self-assembly (DSA) of block co-polymers (BCPs) can realize next-generation lithography for semiconductors and a variety of soft materials. It is imperative to simultaneously achieve many requirements such as a high resolution, orientation control of micro-domains, etch selectivity, rapid and mild annealing, a low cost, and compatibility with manufacturing for developing suitable BCPs. Here, we describe a new design for modified polysiloxane-based BCPs targeted for sub-10-nm-wide lines, which are able to form perpendicularly oriented lamellar structures in thin films. The hydroxyl groups in the side chains introduced in the polysiloxane block provide a good balance with the polystyrene surface free energy, thereby leading to the perpendicular orientation. Moreover, this orientation can be completed in only one minute at 130 °C in an air atmosphere. Oxygen plasma etching for the thin films results in the achievement of a line width of 8.5 nm.

  11. Perpendicularly oriented sub-10-nm block copolymer lamellae by atmospheric thermal annealing for one minute

    PubMed Central

    Seshimo, Takehiro; Maeda, Rina; Odashima, Rin; Takenaka, Yutaka; Kawana, Daisuke; Ohmori, Katsumi; Hayakawa, Teruaki

    2016-01-01

    The directed self-assembly (DSA) of block co-polymers (BCPs) can realize next-generation lithography for semiconductors and a variety of soft materials. It is imperative to simultaneously achieve many requirements such as a high resolution, orientation control of micro-domains, etch selectivity, rapid and mild annealing, a low cost, and compatibility with manufacturing for developing suitable BCPs. Here, we describe a new design for modified polysiloxane-based BCPs targeted for sub-10-nm-wide lines, which are able to form perpendicularly oriented lamellar structures in thin films. The hydroxyl groups in the side chains introduced in the polysiloxane block provide a good balance with the polystyrene surface free energy, thereby leading to the perpendicular orientation. Moreover, this orientation can be completed in only one minute at 130 °C in an air atmosphere. Oxygen plasma etching for the thin films results in the achievement of a line width of 8.5 nm. PMID:26782329

  12. Radiation electrical conductivity of iron tricarbonyl PI-complexes with poly (styrenebutadiene) block copolymers

    SciTech Connect

    Tyutnev, A.P.; Abramov, V.N.; Bronshtein, L.M.; Pozhidaev, E.D.; Saenko, V.V.; Valetskii, P.M.

    1986-04-01

    This paper presents a thorough investigation of the radiation electrical conductivity of an iron-containing block copolymer in which the iron tricarbonyl fragments are built into the main chain of the polymer. The investigations were carried out with a DST-30 poly (styrenebutadiene) block copolymer (30 mass % styrene) and with iron tricarbonyl pi-complexes of this polymer DST-Fe (CO)/sub 3/. The iron tricarbonyl pi-complexes were obtained by reacting the block copolymer with iron dodecacarbonyl in a benzene medium with 10% ethanol in a stream of argon at 80 C. It was found that introduction of iron tricarbonyl into the DST-30 copolymer affects practically all properties of its nonstationary radiation electrical conductivity (NRE). The role of the rapid component of NRE increases with increasing Fe (CO)/sub 3/ content, while the decrease of the delayed component is somewhat slowed down.

  13. Tuning of Polymeric Nanoparticles by Coassembly of Thermoresponsive Polymers and a Double Hydrophilic Thermoresponsive Block Copolymer.

    PubMed

    Zhang, Qilu; Voorhaar, Lenny; Filippov, Sergey K; Yeşil, Berin Fatma; Hoogenboom, Richard

    2016-05-26

    The coassembly behavior of thermoresponsive statistical copolymers and a double hydrophilic block copolymer having a permanently hydrophilic block and a thermoresponsive block is investigated. By adjusting the hydrophilicity of the thermoresponsive statistical copolymers, hybrid nanoparticles are obtained with various ratios of the two species. Importantly, the size of these nanoparticles can be controlled in between 40 and 250 nm dependent on the TCP and the amount of statistical copolymers in the solution. Simultaneous analysis of static and dynamic light scattering data indicates that the possible structure of nanoparticles varies from hard sphere to less compact architecture and most probably depends on a difference between cloud point temperatures of individual components. This developed coassembly method provides a simple platform for the preparation of defined polymeric nanoparticles. PMID:27144970

  14. Effect of Hydrogen-Bonding Junctions on Microphase Separation in Block Copolymers

    NASA Astrophysics Data System (ADS)

    Stone, Greg; Hedrick, Jim; Nederberg, Fredrik; Balsara, Nitash

    2008-03-01

    The morphology of poly(styrene-block- trimethylene carbonate) (PS-PTMC) copolymers with and without thiourea groups at the junction between the blocks was studied by a combination of small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The thiourea groups are known to exhibit inter-molecular hydrogen bonding. We demonstrate that the presence of thiourea groups results in increased segregation between PS and PTMC blocks. We focus on symmetric systems with total molecular weights in the 5 kg/mol range. In conventional block copolymers without hydrogen bonding groups it is difficult to obtain strong segregation in low molecular weight systems because the product chi*N controls segregation (chi is the Flory-Huggins interaction parameter and N is the number of monomers per chain). The incorporation of hydrogen bonding groups may provide a route for the generation of patterns with small, sharply defined features using block copolymers.

  15. Control of Crystallization to Promote Microphase Separation in Fully Conjugated Block Copolymers

    NASA Astrophysics Data System (ADS)

    Lee, Youngmin; Le, Thinh P.; Seibers, Zach; Kilbey, S. Michael, II; Wang, Qing; Gomez, Enrique D.

    Donor -acceptor fully conjugated block copolymers, where donor and acceptor conjugated polymers are covalently bonded together, are interesting as single-component active-layer materials for photovoltaics because it can adopt mesoscale microphase separated structures with length scales comparable to the exciton diffusion length. Nevertheless, due to the strong crystallization of poly(3-hexylthiophene-2,5-diyl) (P3HT), morphologies of fully conjugated block copolymers containing P3HT are predominantly driven by crystallization as opposed to microphase separation. We control the crystallization in block copolymers to promote microphase separation in fully conjugated block copolymers through the addition of small amounts of 3-octylthiophene to the polymerization of P3HT. Poly(3-hexylthiophene-2,5-diyl- r-3-octylthiophene-2,5-diyl)-block-poly((9,9-dioctylfluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5',5''-diyl) (P3HT- b-PFTBT) copolymers were prepared by Grignard metathesis for the alkylthiophene block followed by chain extension through a Suzuki-Miyaura polycondensation. We compare the crystallization, self-assembly and performance in devices of P3HT-b-PFTBT with a few mole percent of 3-octylthiophene in the P3HT block. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831.

  16. Interactions between plasma and block copolymers used in directed self-assembly patterning

    NASA Astrophysics Data System (ADS)

    Sirard, Stephen; Azarnouche, Laurent; Gurer, Emir; Durand, William; Maher, Michael; Mori, Kazunori; Blachut, Gregory; Janes, Dustin; Asano, Yusuke; Someya, Yasunobu; Hymes, Diane; Graves, David; Ellison, Christopher J.; Willson, C. Grant

    2016-03-01

    The directed self-assembly (DSA) of block copolymers offers a promising route for scaling feature sizes below 20 nm. At these small dimensions, plasmas are often used to define the initial patterns. It is imperative to understand how plasmas interact with each block in order to design processes with sufficient etch contrast and pattern fidelity. Symmetric lamella forming block copolymers including, polystyrene-b-poly(methyl methacrylate) and several high-χ silicon-containing and tin-containing block copolymers were synthesized, along with homopolymers of each block, and exposed to various oxidizing, reducing, and fluorine-based plasma processes. Etch rate kinetics were measured, and plasma modifications of the materials were characterized using XPS, AES, and FTIR. Mechanisms for achieving etch contrast were elucidated and were highly dependent on the block copolymer architecture. For several of the polymers, plasma photoemissions were observed to play an important role in modifying the materials and forming etch-resistant protective layers. Furthermore, it was observed for the silicon- and tin-containing polymers that an initial transient state exists, where the polymers exhibit an enhanced etch rate, prior to the formation of the etch-resistant protective layer. Plasma developed patterns were demonstrated for the differing block copolymer materials with feature sizes ranging from 20 nm down to approximately 5 nm.

  17. Low-Temperature Processable Block Copolymers That Preserve the Function of Blended Proteins.

    PubMed

    Iwasaki, Yasuhiko; Takemoto, Kyohei; Tanaka, Shinya; Taniguchi, Ikuo

    2016-07-11

    Low-temperature processable polymers have attracted increasing interest as ecological materials because of their reduced energy consumption during processing and suitability for making composites with heat-sensitive biomolecules at ambient temperature. In the current study, low-temperature processable biodegradable block copolymers were synthesized by ring-opening polymerization of l-lactide (LLA) using polyphosphoester as a macroinitiator. The polymer films could be processed under a hydraulic pressure of 35 MPa. The block copolymer films swelled in water because the polyphosphoester block was partially hydrated. Interestingly, the swelling ratio of the films changed with temperature. The pressure-induced order-to-disorder transition of the block copolymers was characterized by small-angle X-ray scattering; a crystallinity reduction in the block copolymers was observed after application of pressure. The crystallinity of the block copolymers was recovered after removing the applied pressure. The Young's modulus of the block copolymer films increased as the LLA unit content increased. Moreover, the modulus did not change after multiple processing cycles and the recyclability of the block copolymers was also confirmed. Finally, polymer films with embedded proteinase K as a model protein were prepared. The activity of catalase loaded into the polymer films was evaluated after processing at different temperatures. The activity of catalase was preserved when the polymer films were processed at room temperature but was significantly reduced after high-temperature processing. The suitability of low-temperature processable biodegradable polymers for making biofunctional composites without reducing protein activity was clarified. These materials will be useful for biomedical and therapeutic applications. PMID:27280847

  18. Surface affinity role in graphoepitaxy of lamellar block copolymers

    NASA Astrophysics Data System (ADS)

    Claveau, G.; Quemere, P.; Argoud, M.; Hazart, J.; Pimenta Barros, P.; Sarrazin, A.; Posseme, N.; Tiron, R.; Chevalier, X.; Nicolet, C.; Navarro, C.

    2016-03-01

    Overcoming the optical limitations of 193nm immersion lithography can be achieved using Directed Self Assembly (DSA) of block-copolymers (BCPs) as a low-cost and versatile complementary technique. The goal of this paper is to investigate the potential of DSA to address line and space (L/S) high resolution patterning by performing the density multiplication of lines with the graphoepitaxy approach. As surface affinity is a key parameter in self-assembly, three variations, or "flavors", of DSA template affinity are investigated regarding several success criteria such as morphology control or defectivity. More precisely, both the methodology to register DSA defects and the impact of process parameters on defectivity are detailed. Using the 300mm pilot line available in LETI and Arkema's advanced materials, we investigate process optimization of DSA line/space patterning of a 38nm period lamellar PS-b-PMMA BCP (L38). For this study, our integration scheme, depicted in figure 2-1, is based on BCP self-assembly inside organic hard mask guiding patterns obtained using 193i nm lithography. Defect analysis coupled with the fine tuning of process parameters (annealing, brush material) provided the optimum conditions for the L38 self-assembly. Using such conditions, DSA using the three affinity flavors is investigated by means of SEM top-view and cross-section review. Lithographic performances of one selected flavor are then evaluated with the comparison of Process Windows (PWs) function of either commensurability, morphology or LWR. This work is a first step in finding the best process for an industrial graphoepitaxy approach.

  19. Preparation of Pickering double emulsions using block copolymer worms.

    PubMed

    Thompson, Kate L; Mable, Charlotte J; Lane, Jacob A; Derry, Mathew J; Fielding, Lee A; Armes, Steven P

    2015-04-14

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)-poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers. PMID:25834923

  20. Preparation of Pickering Double Emulsions Using Block Copolymer Worms

    PubMed Central

    2015-01-01

    The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)–poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers. PMID:25834923

  1. Controlled self-assembly of conjugated rod-coil block copolymers for applications in organic optoelectronics

    NASA Astrophysics Data System (ADS)

    Tao, Yuefei

    Organic electronics are of great interest in manufacturing light weight, mechanical flexible, and inexpensive large area devices. While significant improvements have been made over the last several years and it is now clear that morphology on the lengthscale of exciton diffusion (10nm) is of crucial importance, a clear relationship between structure and device properties has not emerged. This lack of understanding largely emerges from an inability to control morphology on this lengthscale. This thesis will center around an approach, based on block copolymer self-assembly, to generate equilibrium nanostructures on the 10 nm lengthscale of exciton diffusion and study their effects on device performance. Self-assembly of semiconducting block copolymers is complicated by the non-classical chain shape of conjugated polymers. Unlike classical polymers, the chains do not assume a Gaussian coil shape which is stretched near block copolymer interfaces, instead the chains are elongated and liquid crystalline. Previous work has demonstrated how these new molecular interactions and shapes control the phase diagram of so-called rod-coil block copolymers. Here, we will focus on controlling domain size, orientation, and chemical structure. While domain size can be controlled directly through molecular weight, this requires significant additional synthesis of domain size is to be varied. Here, the domain size is controlled by blending homopolymers into a self-assembling rod-coil block copolymer. When coil-like blocks are incorporated, the domains swell, as expected. When rod-like blocks are incorporated, they interdigitate with the rods of the block copolymers. This results in an increase in interfacial area which forces the coils to rearrange and an overall decrease in domain size with increasing rod content. Control over lamellar orientation is crucial in order to design and control charge transport pathways and exciton recombination or separation interfaces. While numerous

  2. Carbon nanotubes with small and tunable diameters from poly(ferrocenylsilane)-block-polysiloxane diblock copolymers.

    PubMed

    Lu, Jennifer Q; Rider, David A; Onyegam, Emanuel; Wang, Hai; Winnik, Mitchell A; Manners, Ian; Cheng, Qian; Fu, Qiang; Liu, Jie

    2006-05-23

    Iron-containing nanostructures produced from various self-assembled poly(ferrocenylsilane)-block-polysiloxane thin films are catalytically active for the initiation and growth of high density, small diameter carbon nanotubes (CNTs). Moreover, the tube diameter and density can be tuned by adjusting the chain lengths of the block copolymer. Iron-containing nanostructures from poly(ferrocenylmethylethylsilane)-b-poly(methylvinylsiloxane) polymer with 25 repeat units of an iron-containing segment and 265 repeat units of a non-iron-containing segment are able to produce CNTs with diameters around or less than 1 nm. Lithographically selective growth of CNTs across a large surface area has been demonstrated using this polymer system. Under the same growth condition, it has been found that the yield of defect-free CNTs varies with the size of the catalytically active nanostructures, which are dictated by the chain lengths of the two blocks. This result indicates that, for a specific-sized catalyst nanocluster, a unique set of growth conditions is required for synthesizing high yield, defect-free CNTs. This finding further addresses the importance of using uniform-sized catalyst-containing nanostructures for consistently achieving high-yield and high-quality CNTs with a minimum number of defects and amount of amorphous carbon. PMID:16700610

  3. Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

    NASA Technical Reports Server (NTRS)

    Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

    2002-01-01

    It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

  4. Poly(vinylidene fluoride)/nickel nanocomposites from semicrystalline block copolymer precursors

    NASA Astrophysics Data System (ADS)

    Voet, Vincent S. D.; Tichelaar, Martijn; Tanase, Stefania; Mittelmeijer-Hazeleger, Marjo C.; ten Brinke, Gerrit; Loos, Katja

    2012-12-01

    The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric β-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the β-crystalline phase are conserved during the etching procedure and electroless nickel deposition.The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric β-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the β-crystalline phase are conserved during the etching procedure and electroless nickel deposition. Electronic supplementary information (ESI) available

  5. Rheology, Morphology and Phase Behavior in Amphiphilic Block Copolymer/microemulsion Systems

    NASA Astrophysics Data System (ADS)

    Gottlieb, Moshe; Braun, Liora; Zhang, Zeng-Rong

    2000-03-01

    Joining together by means of covalent bonds hydrophobic and hydrophilic entities on the same molecule gives rise to materials with interesting properties in aqueous systems or in the presence of mixed solvents such as water/oil microemulsions. In this paper we describe the rheological properties of a synthetic amphiphilic block copolymer dissolved in a water-in-oil microemulsion. The block copolymer is an ABA type copolymer composed of poly(oxyethylene) (PEO) as the hydrophilic A block and poly(dimethyl siloxane) (PDMS) as the hydrophobic center B block. Different polymers have been prepared with a B block of D_p=160 and three different sizes of the A blocks with D_p= 10, 45, and 120 respectively. The resulting copolymer is insoluble in water and hardly soluble in decane (good solvent for the PDMS). In the presence of water in oil microemulsion stabilized by the small molecular weight surfactant AOT a one-phase region is maintained when the copolymer is added. Yet, peculiar rheological behavior is observed. For constant water-microemulsion concentration (φ) addition of polymer increases the system viscosity as expected. Yet, the lower φ the higher the viscosity and at high φ the effect of polymer addition is quite low.

  6. Frank-Kasper sigma phase stabilized by tailored architectures of block copolymers

    NASA Astrophysics Data System (ADS)

    Li, Weihua; Liu, Meijiao; Xie, Nan; Qiu, Feng; Shi, An-Chang

    Block copolymer self-assembly forms diverse interesting ordered morphologies, of which the spherical phase is of particular interest because it resembles the similar space symmetry as atomic crystals and has a tunable period on nanoscale. Moreover, the packing lattice of spherical domains dictated by the adjustable competition between the entropic and interfacial energies is programmable. For AB diblock copolymers, it has been known that the stable spherical phase is mainly bcc except for a very narrow region of fcc at the vicinity of the order-disorder transition. When introducing variable number of blocks and architectures to form complex AB-type block copolymers, the A15 phase was predicted as stable. However, a striking experiment observed a new spherical phase, the complex Frank-Kasper sigma phase that consists of 30 spheres in a unit cell, in the PI-b-PLA diblock copolymer as well as a SISO tetrablock terpolymer. Inspired by this experiment, we studied the stability of all known spherical phases of fcc, bcc, A15 and sigma in various block copolymers including conformationally asymmetric AB diblock, ABm miktoarm, and BABC tetrablock copolymers. We have revealed the formation mechanism of the nonclassical A15 and sigma phases due to the tailored architectures.

  7. ABC triblock surface active block copolymer with grafted ethoxylated fluoroalkyl amphiphilic side chains for marine antifouling/fouling-release applications.

    PubMed

    Weinman, Craig J; Finlay, John A; Park, Daewon; Paik, Marvin Y; Krishnan, Sitaraman; Sundaram, Harihara S; Dimitriou, Michael; Sohn, Karen E; Callow, Maureen E; Callow, James A; Handlin, Dale L; Willis, Carl L; Kramer, Edward J; Ober, Christopher K

    2009-10-20

    An amphiphilic triblock surface-active block copolymer (SABC) possessing ethoxylated fluoroalkyl side chains was synthesized through the chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene polymer precursor. Bilayer coatings on glass slides consisting of a thin layer of the amphiphilic SABC spray coated on a thick layer of a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) thermoplastic elastomer were prepared for biofouling assays with the green alga Ulva and the diatom Navicula. Dynamic water contact angle analysis and X-ray photoelectron spectroscopy (XPS) were used to characterize the surfaces. Additionally, the effect of the Young's modulus of the coating on the release properties of sporelings (young plants) of the green alga Ulva was examined through the use of two different SEBS thermoplastic elastomers possessing modulus values of an order of magnitude in difference. The amphiphilic SABC was found to reduce the settlement density of zoospores of Ulva as well as the strength of attachment of sporelings. The attachment strength of the sporelings was further reduced for the amphiphilic SABC on the "low"-modulus SEBS base layer. The weaker adhesion of diatoms, relative to a PDMS standard, further highlights the antifouling potential of this amphiphilic triblock hybrid copolymer. PMID:19821626

  8. Time-resolved SANS studies on block copolymer micelles with varying core-solvent interactions

    NASA Astrophysics Data System (ADS)

    Cooksey, Tyler; Singh, Avantika; Marquez, Maria; Robertson, Megan

    The self-assembly of block copolymer micelles occurs through a relaxation process dominated by the exchange of individual polymer chains. The objective of this work is to probe the single chain exchange of block copolymer micelles with varying core-solvent interactions, utilizing time-resolved neutron scattering (TR-SANS). The interactions between the core-forming polymer and the solvent has many implications for the micelle structure, including the aggregation number, micelle size, and interfacial tension. However, few studies have investigated the effect of the core polymer-solvent interactions on the dynamics of micelle formation. We will focus our study on poly(epsilon-caprolactone-block-ethylene oxide) block copolymers forming micelle structures in mixtures of water and tetrahydrofuran (THF). It was observed that changing the THF concentration, which varies the degree of repulsion between the core and solvent, greatly influences the single chain exchange rate in this system.

  9. Hemocompatibility of styrenic block copolymers for use in prosthetic heart valves.

    PubMed

    Brubert, Jacob; Krajewski, Stefanie; Wendel, Hans Peter; Nair, Sukumaran; Stasiak, Joanna; Moggridge, Geoff D

    2016-02-01

    Certain styrenic thermoplastic block copolymer elastomers can be processed to exhibit anisotropic mechanical properties which may be desirable for imitating biological tissues. The ex-vivo hemocompatibility of four triblock (hard-soft-hard) copolymers with polystyrene hard blocks and polyethylene, polypropylene, polyisoprene, polybutadiene or polyisobutylene soft blocks are tested using the modified Chandler loop method using fresh human blood and direct contact cell proliferation of fibroblasts upon the materials. The hemocompatibility and durability performance of a heparin coating is also evaluated. Measures of platelet and coagulation cascade activation indicate that the test materials are superior to polyester but inferior to expanded polytetrafluoroethylene and bovine pericardium reference materials. Against inflammatory measures the test materials are superior to polyester and bovine pericardium. The addition of a heparin coating results in reduced protein adsorption and ex-vivo hemocompatibility performance superior to all reference materials, in all measures. The tested styrenic thermoplastic block copolymers demonstrate adequate performance for blood contacting applications. PMID:26704549

  10. Processing-structure-mechanical Property Relationships of Semicrystalline Polyolefin-based Block Copolymers

    SciTech Connect

    Deplace, F.; Wang, Z; Lynd, N; Hotta, A; Rose, J; Hustad, P; Tian, J; Ohtaki, H; Coates, J; et. al.

    2010-01-01

    The incremental plastic deformation of the crystals of block copolymers made of semicrystalline polypropylene endblocks and amorphous ethylene-r-propylene midblocks occurring during step cycle tensile tests has dramatic effects on the stress-strain curves. This can be understood from the evolution of the morphology and of the microstructure of the crystalline blocks revealed by X-ray scattering experiments.

  11. Multi-block sulfonated poly(phenylene) copolymer proton exchange membranes

    DOEpatents

    Fujimoto, Cy H.; Hibbs, Michael; Ambrosini, Andrea

    2012-02-07

    Improved multi-block sulfonated poly(phenylene) copolymer compositions, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cells, in electrode casting solutions and electrodes. The multi-block architecture has defined, controllable hydrophobic and hydrophilic segments. These improved membranes have better ion transport (proton conductivity) and water swelling properties.

  12. Solvent vapor induced morphology variation in thin films of PS-b-PLA copolymers

    NASA Astrophysics Data System (ADS)

    Foote, Lauren; Heres, Maximilian; Kinsey, Thomas; Sangoro, Joshua

    Molecular dynamics in thin films of PS-b-PLA copolymers annealed by solvent vapor annealing is investigated using broadband dielectric spectroscopy, atomic force microscopy and ellipsometry. Impact of morphology changes on molecular dynamics are analyzed. The results of this study are discussed within the framework of current understanding of morphology control of copolymer thin films.

  13. Melt and Solid-State Structures of Polydisperse Polyolefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Register, Richard; Li, Sheng

    2013-03-01

    Recent developments in coordinative chain transfer polymerization have enabled the synthesis of ethylene-co-octene block copolymers, where the blocks are either crystallizable (an ethylene-co-octene random copolymer block with low octene content) or amorphous (analogous block with high octene content). With a suitable choice of catalyst type(s) and reactor train configuration, accessible chain architectures include diblock, where each block ideally has the most-probable distribution of chain lengths, and multiblock, where both the individual blocks and the number of blocks per chain follow the most-probable distribution. With a sufficiently large interblock octene differential, block copolymers of both architectures, containing roughly equal masses of the two types of block, self-assemble in the melt into well-ordered lamellar structures, despite the large polydispersity. Interblock mixing, induced by the modest Flory interaction parameter and the broad distribution of block lengths, yields an enormous domain spacing (> 100 nm) despite the relatively low average block molecular weights (< 50 kg/mol). Extensive interblock mixing also allows the polyethylene crystals to grow freely and nearly isotropically across the domain interfaces, while preserving the domain structure present in the melt; in the solid state, the optical and x-ray contrasts between dissimilar domains are greatly enhanced due to their different levels of crystallinity. (Work conducted in collaboration with Jeffrey Weinhold, Philip Hustad, and Brian Landes of Dow Chemical Core R&D.) Support from the NSF Polymers Program (DMR-1003942).

  14. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    SciTech Connect

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-15

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol–gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated. - Graphical abstract: One-pot amorphous MnO{sub 2} supported on mesoporous anataseTiO{sub 2}. - Highlights: • Mesoporous manganese titanium oxides were synthesized using block copolymer. • Block copolymers form complexes with Mn{sup 2+} from MnCl{sub 2}. • With block copolymer, manganese oxide can be dispersed around the titania crystallites. • With Mn(acac){sub 2}, manganese is dispersed inside titania. • MnOOH crystallizes outside mesoporous titania during hydrothermal treatment.

  15. Structure and ionic conductivity of block copolymer electrolytes over a wide salt concentration range

    NASA Astrophysics Data System (ADS)

    Chintapalli, Mahati; Le, Thao; Venkatesan, Naveen; Thelen, Jacob; Rojas, Adriana; Balsara, Nitash

    Block copolymer electrolytes are promising materials for safe, long-lasting lithium batteries because of their favorable mechanical and ion transport properties. The morphology, phase behavior, and ionic conductivity of a block copolymer electrolyte, SEO mixed with LiTFSI was studied over a wide, previously unexplored salt concentration range using small angle X-ray scattering, differential scanning calorimetry and ac impedance spectroscopy, respectively. SEO exhibits a maximum in ionic conductivity at twice the salt concentration that PEO, the homopolymer analog of the ion-containing block, does. This finding is contrary to prior studies that examined a more limited range of salt concentrations. In SEO, the phase behavior of the PEO block and LiTFSI closely resembles the phase behavior of homopolymer PEO and LiTFSI. The grain size of the block copolymer morphology was found to decrease with increasing salt concentration, and the ionic conductivity of SEO correlates with decreasing grain size. Structural effects impact the ionic conductivity-salt concentration relationship in block copolymer electrolytes. SEO: polystyrene-block-poly(ethylene oxide); also PS-PEO LiTFSI: lithium bis(trifluoromethanesulfonyl imide

  16. Instantaneous Directional Growth of Block Copolymer Nanowires During Heterogeneous Radical Polymerization (HRP).

    PubMed

    Lu, Chunliang; Urban, Marek W

    2016-04-13

    Polymeric nanowires that consist of ultrahigh molecular weight block copolymers were instantaneously prepared via one-step surfactant-free heterogeneous radical polymerization (HRP). Under heterogeneous reaction and initiator-starvation conditions, the sequential copolymerization of hydrophilic and hydrophobic monomers facilitates the formation of amphiphilic ultrahigh molecular weight block copolymers, which instantaneously assemble to polymeric nanowires. As polymerization progresses, initially formed nanoparticles exhibit the directional growth due to localized repulsive forces of hydrophilic blocks and confinement of the hydrophobic blocks that adopt favorable high aspect ratio nanowire morphologies. Using one-step synthetic approach that requires only four ingredients (water as a solvent, two polymerizable monomers (one hydrophilic and one hydrophobic), and water-soluble initiator), block copolymer nanowires ∼70 nm in diameter and hundreds of microns in length are instantaneously grown. For example, when 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and styrene (St) were copolymerized, high aspect ratio nanowires consist of ultrahigh (>10(6) g/mol) molecular weight pDMAEMA-b-St block copolymers and the presence of temperature responsive pDMAEMA blocks facilitates nanowire diameter changes as a function of temperature. These morphologies may serve as structural components of the higher order biological constructs at micro and larger length scales, ranging from single strand nanowires to engineered biomolecular networks capable of responding to diverse and transient environmental signals, and capable of dimensional changes triggered by external stimuli. PMID:27002238

  17. Thermosensitive PNIPAM-b-HTPB block copolymer micelles: molecular architectures and camptothecin drug release.

    PubMed

    Luo, Yan-Ling; Yang, Xiao-Li; Xu, Feng; Chen, Ya-Shao; Zhang, Bin

    2014-02-01

    Two kinds of thermo-sensitive poly(N-isoproplacrylamide) (PNIPAM) block copolymers, AB4 four-armed star multiblock and linear triblock copolymers, were synthesized by ATRP with hydroxyl-terminated polybutadiene (HTPB) as central blocks, and characterization was performed by (1)H NMR, FT-IR and SEC. The multiblock copolymers could spontaneously assemble into more regular spherical core-shell nanoscale micelles than the linear triblock copolymer. The physicochemical properties were detected by a surface tension technique, nano particle analyzer, TEM, DLS and UV-vis measurements. The multiblock copolymer micelles had lower critical micelle concentration than the linear counterpart, TEM size from 100 to 120 nm and the hydrodynamic diameters below 150 nm. The micelles exhibited thermo-dependent size change, with low critical solution temperature about 33-35 °C. The characteristic parameters were affected by the composition ratios, length of PNIPAM blocks and molecular architectures. The camptothecin release demonstrated that the drug release was thermo-responsive, accompanied by the temperature-induced structural changes of the micelles. MTT assays were performed to evaluate the biocompatibility or cytotoxicity of the prepared copolymer micelles. PMID:24184534

  18. Self-assembled incorporation of modulated block copolymer nanostructures in phase-change memory for switching power reduction.

    PubMed

    Park, Woon Ik; You, Byoung Kuk; Mun, Beom Ho; Seo, Hyeon Kook; Lee, Jeong Yong; Hosaka, Sumio; Yin, You; Ross, C A; Lee, Keon Jae; Jung, Yeon Sik

    2013-03-26

    Phase change memory (PCM), which exploits the phase change behavior of chalcogenide materials, affords tremendous advantages over conventional solid-state memory due to its nonvolatility, high speed, and scalability. However, high power consumption of PCM poses a critical challenge and has been the most significant obstacle to its widespread commercialization. Here, we present a novel approach based on the self-assembly of a block copolymer (BCP) to form a thin nanostructured SiOx layer that locally blocks the contact between a heater electrode and a phase change material. The writing current is decreased 5-fold (corresponding to a power reduction by 1/20) as the occupying area fraction of SiOx nanostructures is increased from a fill factor of 9.1% to 63.6%. Simulation results theoretically explain the current reduction mechanism by localized switching of BCP-blocked phase change materials. PMID:23451771

  19. Ultrasmooth Polydopamine Modified Surfaces for Block Copolymer Nanopatterning on Flexible Substrates.

    PubMed

    Cho, Joon Hee; Katsumata, Reika; Zhou, Sunshine X; Kim, Chae Bin; Dulaney, Austin R; Janes, Dustin W; Ellison, Christopher J

    2016-03-23

    Nature has engineered universal, catechol-containing adhesives which can be synthetically mimicked in the form of polydopamine (PDA). In this study, PDA was exploited to enable the formation of block copolymer (BCP) nanopatterns on a variety of soft material surfaces. While conventional PDA coating times (1 h) produce a layer too rough for most applications of BCP nanopatterning, we found that these substrates could be polished by bath sonication in a weakly basic solution to form a conformal, smooth (root-mean-square roughness ∼0.4 nm), and thin (3 nm) layer free of large prominent granules. This chemically functionalized, biomimetic layer served as a reactive platform for subsequently grafting a surface neutral layer of poly(styrene-random-methyl methacrylate-random-glycidyl methacrylate) to perpendicularly orient lamellae-forming poly(styrene-block-methyl methacrylate) BCP. Moreover, scanning electron microscopy observations confirmed that a BCP nanopattern on a poly(ethylene terephthalate) substrate was not affected by bending with a radius of ∼0.5 cm. This procedure enables nondestructive, plasma-free surface modification of chemically inert, low-surface energy soft materials, thus overcoming many current chemical and physical limitations that may impede high-throughput, roll-to-roll nanomanufacturing. PMID:26942554

  20. Thermal Manipulation of Block Copolymer Morphology by Focused Laser Spike (FLaSk) Annealing

    NASA Astrophysics Data System (ADS)

    Singer, Jonathan; Gotrik, Kevin; Kooi, Steven; Ross, Caroline; Thomas, Edwin

    2011-03-01

    Block copolymer (BCP) thin films have a high potential as a pattern transfer medium for ultra-fine (<10nm) features. We introduce a novel technique for performing rapid local annealing of BCP films by focused laser spike (FLaSk) heating using visible wavelengths. This process may be viewed as imposing a local instantaneous landscape in both block mobilities and interaction parameters corresponding to the temperature profile. By controlling the duration and intensity of the dose, either the rapid local perfection of the equilibrium microdomain morphology or the controlled incorporation of metastable architectures is possible. Moreover, the ultra-short FLaSk process can limit polymer degradation, allowing faster microdomain manipulation by enabling higher temperature anneals. Utilization of a direct write stage allows for deliberate control of arbitrary thermal patterns and subsequent BCP ordering, with line width near the diffraction limit. FLaSk can be applied to nearly any BCP system and performed with other ordering techniques. Direct write experiments were combined with thermal finite elements simulations to probe the various material and process parameters necessary to enhance control of spherical and cylindrical BCPs and address challenges such as the use of thicker films. This research was supported in part by ARO contract W911NF-07-D-0004. JS was supported by the DOD through the NDSEG Program.

  1. Order-Disorder Transitions in Cross-Linked Block Copolymer Solids

    SciTech Connect

    Das, J.

    2005-01-12

    With a view toward creating solid block copolymers wherein the order-disorder transition can be accessed many times they investigated the nature of order-disorder transitions in cross-linked diblock copolymer melts using synergistic theory and experiment. A mean-field theory based on a coarse grained free-energy and the Random Phase Approximation (RPA) is developed for the system of interest. The quenched distribution of cross-links is averaged using the replica method. The phase behavior of a particular A-B block copolymer melt with a randomly cross-linked B-Block is determined as a function of the Florry-Huggins interaction parameter ({chi}) and the average number of cross-links per chain N{sub c}. They find for a cross-link density greater than N*{sub c} the B monomers are localized within a region of size {zeta} {approx} (N{sub c} - N*{sub c}){sup -1/2}. The cross-links strongly oppose ordering in the system as {zeta} becomes comparable to the radius of gyration of the block copolymer chain. As such the order-disorder transition temperature T{sub ODT} decreases precipitously when N{sub c} > N*{sub c}. When N{sub c} < N*{sub c}, T{sub ODT} increases weakly with N{sub c}. Experiments were conducted on cross-linked polystyrene-block-polyisoprene copolymer samples wherein the polyisoprene block was selectively cross-linked at a temperature well above the order-disorder transition temperature of the pure block copolymer. Small angle X-ray scattering (SAXS) and birefringence measurements on the cross-linked samples are consistent with the theoretical prediction. T{sub ODT} decreases rapidly when the cross-linking density exceeds the critical cross-linking density.

  2. Vertical Continuity and Alignment of Block Copolymer Domains by Kinetically Controlled Electrospray Deposition

    NASA Astrophysics Data System (ADS)

    Hu, Hanqiong; Woo, Youngwoo; Feng, Xunda; Osuji, Chinedum; Osuji Lab Team

    2015-03-01

    We report the fabrication of vertically aligned cylindrical block copolymer (BCP) domains using continuous electrospray deposition (ESD) onto bare wafer surfaces. The out-of-plane orientation of hexagonally packed styrene cylinders was achieved in a ``fast-wet'' deposition regime where rapid evaporation of solvent in droplets of polymer solution drove the vertical alignment of SBS domains. The deposition conditions were optimized such that thermally activated crosslinking of the polybutadiene matrix provided kinetic control of the morphology, locking in the vertical alignment and preventing relaxation of the system to its preferred parallel orientation on the non-treated substrate. Physically continuous and vertically oriented domains is achieved over several microns of film thickness. We describe the effects of flow rate, collection distance and substrate temperature on thin film morphology and demonstrate selective etching capabilities. The ability of ESD to fabricate well-ordered and aligned BCP films on non-treated substrates, the low utilization of material relative to spin-coating and the continuous nature of the deposition may open up new opportunities for BCP thin films. We are exploring ESD as a new platform for sequential deposition of BCPs with different functionalities.

  3. Directed block copolymer self-assembly implemented via surface-embedded electrets

    NASA Astrophysics Data System (ADS)

    Wu, Mei-Ling; Wang, Dong; Wan, Li-Jun

    2016-02-01

    Block copolymer (BCP) nanolithography is widely recognized as a promising complementary approach to circumvent the feature size limits of conventional photolithography. The directed self-assembly of BCP thin film to form ordered nanostructures with controlled orientation and localized pattern has been the key challenge for practical nanolithography applications. Here we show that BCP nanopatterns can be directed on localized surface electrets defined by electron-beam irradiation to realize diverse features in a simple, effective and non-destructive manner. Charged electrets can generate a built-in electric field in BCP thin film and induce the formation of perpendicularly oriented microdomain of BCP film. The electret-directed orientation control of BCP film can be either integrated with mask-based patterning technique or realized by electron-beam direct-writing method to fabricate microscale arbitrary lateral patterns down to single BCP cylinder nanopattern. The electret-directed BCP self-assembly could provide an alternative means for BCP-based nanolithography, with high resolution.

  4. Coarse-grained molecular dynamics modeling of the kinetics of lamellar block copolymer defect annealing

    NASA Astrophysics Data System (ADS)

    Peters, Andrew J.; Lawson, Richard A.; Nation, Benjamin D.; Ludovice, Peter J.; Henderson, Clifford L.

    2016-01-01

    State-of-the-art block copolymer (BCP)-directed self-assembly (DSA) methods still yield defect densities orders of magnitude higher than is necessary in semiconductor fabrication despite free-energy calculations that suggest equilibrium defect densities are much lower than is necessary for economic fabrication. This disparity suggests that the main problem may lie in the kinetics of defect removal. This work uses a coarse-grained model to study the rates, pathways, and dependencies of healing a common defect to give insight into the fundamental processes that control defect healing and give guidance on optimal process conditions for BCP-DSA. It is found that bulk simulations yield an exponential drop in defect heal rate above χN˜30. Thin films show no change in rate associated with the energy barrier below χN˜50, significantly higher than the χN values found previously for self-consistent field theory studies that neglect fluctuations. Above χN˜50, the simulations show an increase in energy barrier scaling with 1/2 to 1/3 of the bulk systems. This is because thin films always begin healing at the free interface or the BCP-underlayer interface, where the increased A-B contact area associated with the transition state is minimized, while the infinitely thick films cannot begin healing at an interface.

  5. Molecular transport through nanoporous silicon nitride membranes produced from self-assembling block copolymers.

    PubMed

    Montagne, Franck; Blondiaux, Nicolas; Bojko, Alexandre; Pugin, Raphaël

    2012-09-28

    To achieve fast and selective molecular filtration, membrane materials must ideally exhibit a thin porous skin and a high density of pores with a narrow size distribution. Here, we report the fabrication of nanoporous silicon nitride membranes (NSiMs) at the full wafer scale using a versatile process combining block copolymer (BCP) self-assembly and conventional photolithography/etching techniques. In our method, self-assembled BCP micelles are used as templates for creating sub-100 nm nanopores in a thin low-stress silicon nitride layer, which is then released from the underlying silicon wafer by etching. The process yields 100 nm thick free-standing NSiMs of various lateral dimensions (up to a few mm(2)). We show that the membranes exhibit a high pore density, while still retaining excellent mechanical strength. Permeation experiments reveal that the molecular transport rate across NSiMs is up to 16-fold faster than that of commercial polymeric membranes. Moreover, using dextran molecules of various molecular weights, we also demonstrate that size-based separation can be achieved with a very good selectivity. These new silicon nanosieves offer a relevant technological alternative to commercially available ultra- and microfiltration membranes for conducting high resolution biomolecular separations at small scales. PMID:22899238

  6. Directed block copolymer self-assembly implemented via surface-embedded electrets

    PubMed Central

    Wu, Mei-Ling; Wang, Dong; Wan, Li-Jun

    2016-01-01

    Block copolymer (BCP) nanolithography is widely recognized as a promising complementary approach to circumvent the feature size limits of conventional photolithography. The directed self-assembly of BCP thin film to form ordered nanostructures with controlled orientation and localized pattern has been the key challenge for practical nanolithography applications. Here we show that BCP nanopatterns can be directed on localized surface electrets defined by electron-beam irradiation to realize diverse features in a simple, effective and non-destructive manner. Charged electrets can generate a built-in electric field in BCP thin film and induce the formation of perpendicularly oriented microdomain of BCP film. The electret-directed orientation control of BCP film can be either integrated with mask-based patterning technique or realized by electron-beam direct-writing method to fabricate microscale arbitrary lateral patterns down to single BCP cylinder nanopattern. The electret-directed BCP self-assembly could provide an alternative means for BCP-based nanolithography, with high resolution. PMID:26876792

  7. Directed block copolymer self-assembly implemented via surface-embedded electrets.

    PubMed

    Wu, Mei-Ling; Wang, Dong; Wan, Li-Jun

    2016-01-01

    Block copolymer (BCP) nanolithography is widely recognized as a promising complementary approach to circumvent the feature size limits of conventional photolithography. The directed self-assembly of BCP thin film to form ordered nanostructures with controlled orientation and localized pattern has been the key challenge for practical nanolithography applications. Here we show that BCP nanopatterns can be directed on localized surface electrets defined by electron-beam irradiation to realize diverse features in a simple, effective and non-destructive manner. Charged electrets can generate a built-in electric field in BCP thin film and induce the formation of perpendicularly oriented microdomain of BCP film. The electret-directed orientation control of BCP film can be either integrated with mask-based patterning technique or realized by electron-beam direct-writing method to fabricate microscale arbitrary lateral patterns down to single BCP cylinder nanopattern. The electret-directed BCP self-assembly could provide an alternative means for BCP-based nanolithography, with high resolution. PMID:26876792

  8. Polythiophene-block-poly(γ-benzyl L-glutamate): Synthesis and study of a new rod-rod block copolymer

    SciTech Connect

    Wu, Zong-Quan; Ono, Robert J.; Chen, Zheng; Li, Zicheng; Bielawski, Christopher W.

    2011-01-01

    Coupling of ethynyl terminated poly(3-hexylthiophene) with azide terminated poly(γ-benzyl L-glutamate) afforded the respective block copolymer in good yield and high purity; this material was found to self assemble into hierarchal structures in solution and in the solid state.

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

    PubMed

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

    2016-08-10

    The ability to fabricate nanostructured films by exploiting the phenomenon of microphase separation has made block copolymers an invaluable tool for a wide array of coating applications. Standard approaches to engineering nanodomains commonly involve the application of organic solvents, either through dissolution or annealing protocols, resulting in the release of volatile organic compounds (VOCs). In this paper, an aqueous-based method of fabricating low-VOC nanostructured block copolymer films is presented. The reported procedure allows for the phase transfer of water insoluble triblock copolymer, poly(styrene-block-2 vinylpyridine-block-ethylene oxide) (PS-b-P2VP-b-PEO), from a water immiscible phase to an aqueous environment with the assistance of a diblock copolymeric phase transfer agent, poly(styrene-block-ethylene oxide) (PS-b-PEO). Phase transfer into the aqueous phase results in self-assembly of PS-b-P2VP-b-PEO into core-shell-corona micelles, which are characterized by dynamic light scattering techniques. The films that result from coating the micellar solution onto Si/SiO2 surfaces exhibit nanoscale features that disrupt the ability of a model foulant, a zoospore of Ulva linza, to settle. The multilayered architecture consists of a pH-responsive P2VP-"shell" which can be stimulated to control the size of these features. The ability of these nanostructured thin films to resist protein adsorption and serve as potential marine antifouling coatings is supported through atomic force microscopy (AFM) and analysis of the settlement of Ulva linza zoospore. Field trials of the surfaces in a natural environment show the inhibition of macrofoulants for 1 month. PMID:27388921

  10. Morphological and physical characterization of poly(styrene-isobutylene-styrene) block copolymers and ionomers thereof

    NASA Astrophysics Data System (ADS)

    Baugh, Daniel Webster, III

    Poly(styrene-isobutylene-styrene) block copolymers made by living cationic polymerization using a difunctional initiator and the sequential monomer addition technique were analyzed using curve-resolution software in conjunction with high-resolution GPC. Fractional precipitation and selective solvent extraction were applied to a representative sample in order to confirm the identity of contaminating species. The latter were found to be low molecular weight polystyrene homopolymer, diblock copolymer, and higher molecular weight segmented block copolymers formed by intermolecular electrophilic aromatic substitution linking reactions occurring late in the polymerization of the styrene outer blocks. Solvent-cast films of poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers and block ionomers were analyzed using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Four block copolymer samples with center block molecular weights of 52,000 g/mol and PS volume fractions (o sbPS) ranging from 0.17 to 0.31 were studied. All samples exhibited hexagonally packed cylinders of PS within the PIB matrix. Cylinder spacing was in the range 32 to 36 nm for most samples, while cylinder diameters varied from 14 to 21 nm. Porod analysis of the scattering data indicated the presence of isolated phase mixing and sharp phase boundaries. PS-PIB-PS block copolymers and ionomers therefrom were analyzed using dynamic mechanical analysis (DMA) and tensile testing. The study encompassed five block copolymer samples with similar PIB center blocks with molecular weights of approx52,000 g/mol and PS weight fractions ranging from 0.127 to 0.337. Ionomers were prepared from two of these materials by lightly sulfonating the PS outer blocks. Sulfonation levels varied from 1.7 to 4.7 mol % and the sodium and potassium neutralized forms were compared to the parent block copolymers. Dynamic mechanical analysis (DMA) of the block copolymer films indicated the existence

  11. The versatility in morphology and physical properties offered by chain shuttled olefin block copolymers

    NASA Astrophysics Data System (ADS)

    Weinhold, Jeffrey

    2014-03-01

    Chain shuttling catalysis enables the production of olefin block copolymers (OBCs) with a wide range of block compositions. Unique morphology and property combinations can be achieved with highly crystalline hard blocks and low crystallinity or fully amorphous soft blocks. The effect of the amount of comonomer in the soft blocks on phase behavior, morphology and properties will be the focus of this presentation. In one class of materials, the soft blocks contain just enough octene comonomer to give elastic behavior but, unlike a random copolymer-based olefin elastomer, the soft segments are held together by thick crystals formed by the hard blocks. In addition to strengthening the network, these crystals provide temperature resistance and, by solidifying at higher temperature, they allow faster product fabrication. Increasing the soft block's octene content yields the next class of materials which have improved compatibility with polypropylene. This property allows the formation of fine, uniformly-dispersed OBC elastomer particles in PP. Since the impact strength of toughened PP increases as the particle size is reduced, a lower amount of elastomer is required to achieve an application's target for toughness. The direct benefit of lower elastomer loading is an increase in modulus, which enables lightweighting in applications. With further increases in the soft block's octene content, the incompatibility between the hard and soft blocks becomes large enough to cause the OBCs to form ordered melt morphologies. In the solid state, the alternating crystalline and amorphous regions have surprisingly large domain spacings and, due to the difference in refractive index between the domains, the periodicity results in a partial photonic band gap for frequencies in the visible spectrum. Comparisons to the morphology of monodisperse block copolymers and the predictions of theories will be presented. Also, the results of an extension to strong segregation theory will be shown

  12. Lateral structuring and stability phenomena induced by block copolymers and core-shell nanogel particles at immiscible polymer/polymer interfaces

    NASA Astrophysics Data System (ADS)

    Gozen, Arif Omer

    We have investigated the parameters such as copolymer/nanoparticle concentration, architecture and molecular weight combined with film thickness, time and temperature in order to develop a molecular-level insight on how lateral interfacial structuring occurs at immiscible polymer/polymer interfaces. I order to develop a molecular-level understanding of how these 'smart' self-assembling materials and core-shell nanogel particles interact both intra- and inter-molecularly and form ordered structures in bulk, as well as at immiscible interfaces, we first focused on the response of core-shell polymer nanoparticles, designated CSNGs, composed of a cross-linked divinylbenzene core and poly(methyl methacrylate) (PMMA) arms as they segregate from PMMA homopolymer. We have demonstrated that these nanogel particles exhibit autophobic character when dispersed in high molecular weight homopolymer matrices and segregate to the interface with another fluid. We have further explored the migration of these new-generation nanogel particles (CSNG-Rs) segregating from PS homopolymer to PS/PMMA interfaces. Unlike the instability patterns observed with the CSNGs, which exhibit classical nucleation and growth mechanism with circular hole formation, we have observed an intriguing dewetting pattern and CSNG-Rs forming lateral aggregates and tentacle-like structures at the interface. In parallel with our core-shell particle studies, we have also explored the structuring of copolymer molecules that are far from equilibrium in bulk and complex laminate of polymer thin films. Our early triblock copolymer studies have proven that molecular asymmetry has a profound effect on order-disorder transition temperature. We focused primarily on the effect of the copolymer chemical composition (i.e., block sizes) on the dewetting behavior of PS/SM thin films on PMMA. We elucidate the interfacial segregation and concurrent micellization of diblock copolymers in a dynamically evolving environment with

  13. Ordered porous mesostructured materials from nanoparticle-block copolymer self-assembly

    SciTech Connect

    Warren, Scott; Wiesner, Ulrich; DiSalvo, Jr., Francis J

    2013-10-29

    The invention provides mesostructured materials and methods of preparing mesostructured materials including metal-rich mesostructured nanoparticle-block copolymer hybrids, porous metal-nonmetal nanocomposite mesostructures, and ordered metal mesostructures with uniform pores. The nanoparticles can be metal, metal alloy, metal mixture, intermetallic, metal-carbon, metal-ceramic, semiconductor-carbon, semiconductor-ceramic, insulator-carbon or insulator-ceramic nanoparticles, or combinations thereof. A block copolymer/ligand-stabilized nanoparticle solution is cast, resulting in the formation of a metal-rich (or semiconductor-rich or insulator-rich) mesostructured nanoparticle-block copolymer hybrid. The hybrid is heated to an elevated temperature, resulting in the formation of an ordered porous nanocomposite mesostructure. A nonmetal component (e.g., carbon or ceramic) is then removed to produce an ordered mesostructure with ordered and large uniform pores.

  14. Amphiphilic block copolymers in oil-water-surfactant mixtures: efficiency boosting, structure, phase behaviour and mechanism

    NASA Astrophysics Data System (ADS)

    Gompper, G.; Richter, D.; Strey, R.

    2001-10-01

    The effect of amphiphilic block copolymers on the phase behaviour and structure of ternary microemulsions in water, oil and non-ionic surfactant mixtures is reviewed. Recent experiments have revealed that the addition of small amounts of polyethylenepropylene-polyethyleneoxide block copolymer to the ternary systems leads to a dramatic increase in the volumes of oil and water solubilized into a bicontinuous microemulsion for a given surfactant volume fraction. While phase diagrams directly show the power of the amphiphilic block copolymers as efficiency boosters, the theoretical analysis in terms of bending energy discloses the mechanism for the efficiency boosting as due to the variation of the surfactant film curvature elasticity by tethered polymers in the form of mushrooms at the interface. Neutron scattering experiments employing a high-precision two-dimensional contrast variation technique confirm this picture and demonstrate that the polymer molecules uniformly decorate the surfactant film.

  15. Charge transfer in the low-temperature radiolysis of styrene-butadiene block copolymers

    SciTech Connect

    Khatipov, S.A.; Edrisov, A.T.; Milinchuk, V.K.

    1995-05-01

    Radiation-induced conductivity of polystyrene, polybutadiene, and styrene-butadiene block copolymers, resulting from irradiation of the samples with fast electrons of 75 keV energy under vacuum at 100 K, was studied. A negative deviation of the radiation-induced conductivity constant A{sub m} from the corresponding additive values was detected upon varying the composition of block copolymers. It is concluded that the interfacial charge transfer from polystyrene to polybutadiene microdomains occurs in the block copolymers. This conclusion is confirmed by the results of investigations of drift mobility of the charge carriers and effects of donor-acceptor admixtures on the radiation-induced conductivity of the polymers studied.

  16. Efficient Synthesis of Cyclic Block Copolymers by Rotaxane Protocol by Linear/Cyclic Topology Transformation.

    PubMed

    Valentina, Stephanie; Ogawa, Takahiro; Nakazono, Kazuko; Aoki, Daisuke; Takata, Toshikazu

    2016-06-20

    High-yielding synthesis of cyclic block copolymer (CBC) using the rotaxane protocol by linear-cyclic polymer topology transformation was first demonstrated. Initial complexation of OH-terminated sec-ammonium salt and a crown ether was followed by the successive living ring-opening polymerizations of two lactones to a linear block copolymer having a rotaxane structure by the final capping of the propagation end. CBC was obtained in a high yield by an exploitation of the mechanical linkage through the translational movement of the rotaxane component to transform polymer structure from linear to cyclic. Furthermore, the change of the polymer topology was translated into a macroscopic change in crystallinity of the block copolymer. PMID:27037975

  17. Configurational bias Monte Carlo simulation of phase segregation in block copolymer networks.

    PubMed

    Palmer, Kent I; Lastoskie, Christian M

    2004-01-01

    Cross-linked block copolymers are used as adhesives in fiber-reinforced composite material manufactures for automotive applications. Good adhesion between the polymer matrix and fibers in the interphase region is required for the structural integrity of these materials. Experimental evidence indicates that superior adhesion is obtained when phase segregation occurs between the two matrix phase block copolymers. It is therefore desirable to predict the conditions under which phase segregation is expected to occur. Configurational bias Monte Carlo simulations of two-component, trifunctional block copolymer networks were carried out to investigate phase segregation in these materials. The effects of four principal parameters on phase segregation were examined: the weight fractions of the two components, the cross-link length, the connectivity of the network, and the ratio of the square-well interactions. The molecular simulation results confirmed trends observed in laboratory measurements. PMID:15267310

  18. Three-dimensional inverse design of nanopatterns with block copolymers and homopolymers

    NASA Astrophysics Data System (ADS)

    Xu, Dan; Liu, Hong; Zhu, You-Liang; Lu, Zhong-Yuan

    2016-02-01

    We propose a facile inverse design strategy to generate three-dimensional (3D) nanopatterns by using either block copolymers or a binary homopolymer blend via dissipative particle dynamics simulations. We find that the composition window of block copolymers to form a specific 3D morphology can be expanded when the self-assembly of block copolymers is directed by templates. We also find that a binary homopolymer blend can serve as a better candidate in the inverse templating design, since they have similar performances on recovering the target pattern, with much lower cost. This strategy is proved efficient for fabricating templates with desired topographical configuration, and the inverse design idea sheds lights on better control and design of materials with complex nanopatterns.

  19. Three-dimensional inverse design of nanopatterns with block copolymers and homopolymers.

    PubMed

    Xu, Dan; Liu, Hong; Zhu, You-Liang; Lu, Zhong-Yuan

    2016-03-01

    We propose a facile inverse design strategy to generate three-dimensional (3D) nanopatterns by using either block copolymers or a binary homopolymer blend via dissipative particle dynamics simulations. We find that the composition window of block copolymers to form a specific 3D morphology can be expanded when the self-assembly of block copolymers is directed by templates. We also find that a binary homopolymer blend can serve as a better candidate in the inverse templating design, since they have similar performances on recovering the target pattern, with much lower cost. This strategy is proved efficient for fabricating templates with desired topographical configuration, and the inverse design idea sheds lights on better control and design of materials with complex nanopatterns. PMID:26880143

  20. Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures

    PubMed Central

    Connal, Luke A.; Lynd, Nathaniel A.; Robb, Maxwell J.; See, Kimberly A.; Jang, Se Gyu; Spruell, Jason M.

    2012-01-01

    We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, while the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles. In both cases, ordered morphologies templated by the original block copolymer domains were obtained. PMID:23335837

  1. Selective directed self-assembly of coexisting morphologies using block copolymer blends

    NASA Astrophysics Data System (ADS)

    Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

    2016-08-01

    Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.

  2. Surface activity of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers

    SciTech Connect

    Alexandridis, P.; Athanassiou, V.; Fukuda, Shinya; Hatton, T.A. )

    1994-08-01

    The surface tension of aqueous solutions of seven poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) Pluronic copolymers, covering a wide range of molecular weights (3400-14600) and PPO/PEO ratios (0.19-1.79), was determined over the 10[sup [minus]5]-10% w/v concentration range, at two temperatures (25 and 35[degree]C). Two breaks (changes in slope) were observed in the surface tension vs log concentration curve for most of the copolymers. The low-concentration break, occurring at bulk copolymer concentrations of approximately 10[sup [minus]3]%, is believed to originate from rearrangement of the copolymer molecules on the surface at complete coverage of the air/water interface. The breaks at the high-concentration part of the surface tension curve occurred at concentrations that correspond to the critical micellization concentration values as determined by a dye solubilization technique. The surface area per copolymer molecule, A, increased as a function of the number of EO segments, N[sub EO], obeying a scaling law (A [approx] N[sub EO][sup 1/2]) similar to that of lower molecular weight C[sub i]E[sub j] nonionic surfactants. 56 refs., 6 figs., 2 tabs.

  3. Mixing a sol and a precipitate of block copolymers with different block ratios leads to an injectable hydrogel.

    PubMed

    Yu, Lin; Zhang, Zheng; Zhang, Huan; Ding, Jiandong

    2009-06-01

    A facile method to obtain a thermoreversible physical hydrogel was found by simply mixing an aqueous sol of a block copolymer with a precipitate of a similar copolymer but with a different block ratio. Two ABA-type triblock copolymers poly(D,L-lactic acid-co-glycolic acid)-B-poly(ethylene glycol)-B-poly(D,L-lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) were synthesized. One sample in water was a sol in a broad temperature region, while the other in water was just a precipitate. The mixture of these two samples with a certain mix ratio underwent, however, a sol-to-gel-to-precipitate transition upon an increase of temperature. A dramatic tuning of the sol-gel transition temperature was conveniently achieved by merely varying mix ratio, even in the case of a similar molecular weight. Our study indicates that the balance of hydrophobicity and hydrophilicity within this sort of amphiphilic copolymers is critical to the inverse thermal gelation in water resulting from aggregation of micelles. The availability of encapsulation and sustained release of lysozyme, a model protein by the thermogelling systems was confirmed. This "mix" method provides a very convenient approach to design injectable thermogelling biomaterials with a broad adjustable window, and the novel copolymer mixture platform is potentially used in drug delivery and other biomedical applications. PMID:19385649

  4. Collapse transitions in thermosensitive multi-block copolymers: a Monte Carlo study.

    PubMed

    Rissanou, Anastassia N; Tzeli, Despoina S; Anastasiadis, Spiros H; Bitsanis, Ioannis A

    2014-05-28

    Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (AnBn)m consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500-5000 units) and very differing energetic conditions for the two blocks (very good-almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks. PMID:24880322

  5. Collapse transitions in thermosensitive multi-block copolymers: A Monte Carlo study

    SciTech Connect

    Rissanou, Anastassia N.; Tzeli, Despoina S.; Anastasiadis, Spiros H.; Bitsanis, Ioannis A.

    2014-05-28

    Monte Carlo simulations are performed on a simple cubic lattice to investigate the behavior of a single linear multiblock copolymer chain of various lengths N. The chain of type (A{sub n}B{sub n}){sub m} consists of alternating A and B blocks, where A are solvophilic and B are solvophobic and N = 2nm. The conformations are classified in five cases of globule formation by the solvophobic blocks of the chain. The dependence of globule characteristics on the molecular weight and on the number of blocks, which participate in their formation, is examined. The focus is on relative high molecular weight blocks (i.e., N in the range of 500–5000 units) and very differing energetic conditions for the two blocks (very good—almost athermal solvent for A and bad solvent for B). A rich phase behavior is observed as a result of the alternating architecture of the multiblock copolymer chain. We trust that thermodynamic equilibrium has been reached for chains of N up to 2000 units; however, for longer chains kinetic entrapments are observed. The comparison among equivalent globules consisting of different number of B-blocks shows that the more the solvophobic blocks constituting the globule the bigger its radius of gyration and the looser its structure. Comparisons between globules formed by the solvophobic blocks of the multiblock copolymer chain and their homopolymer analogs highlight the important role of the solvophilic A-blocks.

  6. Formation of Nonclassical Ordered Phases of A B -Type Multiarm Block Copolymers

    NASA Astrophysics Data System (ADS)

    Gao, Ya; Deng, Hanlin; Li, Weihua; Qiu, Feng; Shi, An-Chang

    2016-02-01

    The formation of ordered phases from block copolymers is driven by a delicate balance between the monomer-monomer interaction and chain configurational entropy. The configurational entropy can be regulated by designed chain architecture, resulting in a new entropy-driven mechanism to control the self-assembly of ordered phases from block copolymers. An effective routine to regulate the configurational entropy is to utilize multiarm architecture, in which the entropic contribution to the free energy could be qualitatively controlled by the fraction of bridging configurations. As an illustration of this mechanism, the phase behavior of two A B -type multiarm block copolymers, B0-(Bi-Ai) m and (B1-Ai-B2) m where the minority A blocks form cylindrical or spherical domains, are examined using the self-consistent field theory (SCFT). The SCFT results demonstrate that the packing symmetry of the cylinders or spheres can be controlled by the length of the bridging B blocks. Several nonclassical ordered phases, including a novel square array cylinder with p 4 m m symmetry, are predicted to form from the A B -type multiarm block copolymers.

  7. Micelles, Lamellaes and Connected Bilayer Membranes in Block Copolymer Melts, Blends and Solutions

    NASA Astrophysics Data System (ADS)

    Mortensen, Kell

    1997-03-01

    Block copolymers of poly(ethylene oxide), PEO, and poly(propylene oxide), PPO, provide a unique model system for studies of aqueous systems of amphilic macromolecules, as the amphiphilic character can be changed continuously by changing temperature(K Mortensen, W Brown, B. Nordén , Phys. Rev. Letters 13 2340 (1992)) or pressure(K Mortensen, D Schwahn S Janssen Phys. Rev. Letters 71 1728 (1993)). The structural characteristics of aqueous solutions of the PEO-PPO-PEO copolymers and their self-associated assemblies are reviewed(K Mortensen, J. Phys. Cond. Matter 8 A103 (1996)). It is shown by small-angle neutron scattering that at low temperatures and/or concentration the individual copolymers exist in solution as individual unimers. Depending on molecular design, i.e. size of the individual blocks, various aggregates are formed, including spherical, worm-like and disc-shaped micelles. The spherical micelles provide the basis for liquid-crystalline mesophases of cubic structure. The crystallization can be understood as a simple hard-sphere condensation. Worm- or rod-like micelles may form nematic or hexagonally ordered structures, whereas the discs may condense into lamellar phases. While bi-continuous microemulsions frequently appear in ternary phase diagrams of oil, water and low-molecular surfactants, there has only recently been observations of such phases in binary systems of block copolymers and solvent. The first observation was made in an aqueous solution of a low PEO-content PEO-PPO-PEO triblock copolymer(E Hecht, K Mortensen, H Hoffmann, Macromolecules 28 5465, 1995). More recently, the microemulsion sponge phase has been observed in a system of tri-block copolymers dissolved in homopolymers( JH Laurer, JC Fung, JW Sedat, DA Agard, SD Schmit, J Samseth, K Mortensen, RJ Spontak, Langmuir, submitted) and in a ternary systems of diblock copolymer and homopolymers(FS Bates, WW Maurer, PM Lipic MA Hillmyer, KA Almdal, K Mortensen, TP Lodge Science, submitted).

  8. Development of flexible LEO-resistant PI films for space applications using a self-healing mechanism by surface-directed phase separation of block copolymers.

    PubMed

    Fischer, Hartmut R; Tempelaars, Karin; Kerpershoek, Aat; Dingemans, Theo; Iqbal, M; Lonkhuyzen, Henk van; Iwanowsky, Boris; Semprimoschnig, Christopher

    2010-08-01

    Polimide-block-polydimethylsiloxane (PI-b-PDMS) block copolymers have been synthesized from commercially available amino-terminated polysiloxanes with different molecular weights, for use as polymeric materials resistant to the low earth orbit (LEO) space environment. A structural optimization with respect to maximum environmental protection has been performed by varying the PDMS block length as well as the architecture of the block copolymers spanning from multiblock to triblock and star-shaped morphologies. The synthesized polymers and casted films show good mechanical and thermal performance. For block copolymers with a load of 2% PDMS (in the case of the multiblock copolymers), a complete surface coverage of the PDMS has been found. It has been shown that the transfer of the surface enriched PDMS layer into a thin silica layer after atomic oxygen (AO) exposure results in a drastic decrease in AO erosion rate. The silica layer protects the underlying material from oxygen initiated erosion resulting in a drastic decrease of surface roughness. This phenomena is observable for loads as small as 6 wt % PDMS. PMID:20690681

  9. Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

    NASA Astrophysics Data System (ADS)

    Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

    2016-07-01

    Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

  10. Data on macrophage mediated muscle transfection upon delivery of naked plasmid DNA with block copolymers.

    PubMed

    Mahajan, Vivek; Gaymalov, Zagit; Alakhova, Daria; Gupta, Richa; Zucker, Irving H; Kabanov, Alexander V

    2016-06-01

    The data contains 14 figures supporting the research article "Horizontal gene transfer from macrophages to ischemic muscles upon delivery of naked DNA with Pluronic block copolymers" [1]. The data explains the surgical procedure and histological characterization of Murine Hind Limb Ischemia. The data also shows the kinetics of luciferase gene expression, spread of GFP expression through muscle and the colocalization of GFP with cellular markers in ischemic muscles injected with pDNA alone or pDNA/Pluronic. Finally the data shows the effect of Pluronic Block Copolymer to enhance total gene expression (cmv-promoter driven luciferase gene) in coculture of DNA transfected MØs with muscle cells. PMID:27222845

  11. Flow-directed block copolymer micelle morphologies via microfluidic self-assembly.

    PubMed

    Wang, Chih-Wei; Sinton, David; Moffitt, Matthew G

    2011-11-23

    The self-assembly of amphiphilic block copolymers in a gas-liquid microfluidic reactor produces variable, flow-directed micellar morphologies entirely different from off-chip equilibrium structures. A polystyrene-block-poly(acrylic acid) copolymer, which forms exclusively spheres off-chip, generates kinetic cylinders, Y-junctions, bilayers, and networks by a mechanism of collision-coalescence enabled by strong and localized on-chip shear fields. Variation in the size and relative amount of flow-directed nanostructures is achieved by changing the water content and flow rate. These results demonstrate on-chip processing routes to specific functional colloidal nanostructures. PMID:21992654

  12. Chemical composition effects on the crazing of PS-PMMA block copolymers

    NASA Astrophysics Data System (ADS)

    Kim, Won; Han, Junwon; Yang, Hoichang; Ryu, Chang

    2006-03-01

    Using a large scale separation technique adopting interaction chromatography, we have fractionated as-synthesized PS-PMMA block copolymers in terms of the average chemical composition difference, while maintaining the same average molecular weight. Copper grid technique with optical, atomic force and transmission electron microscopy has been employed for the fracture study to reveal how the composition-dependent morphology affect the crazing of the glassy-glassy block copolymers, while maintaining the same level of Chi*N. In addition, we study how the thermal annealing affects the median strains for crazing and catastrophic failure.

  13. Crystalline Oligo(ethylene sulfide) Domains Define Highly Stable Supramolecular Block Copolymer Assemblies.

    PubMed

    Brubaker, Carrie E; Velluto, Diana; Demurtas, Davide; Phelps, Edward A; Hubbell, Jeffrey A

    2015-07-28

    With proper control over copolymer design and solvation conditions, self-assembled materials display impressive morphological variety that encompasses nanoscale colloids as well as bulk three-dimensional architectures. Here we take advantage of both hydrophobicity and crystallinity to mediate supramolecular self-assembly of spherical micellar, linear fibrillar, or hydrogel structures by a family of highly asymmetric poly(ethylene glycol)-b-oligo(ethylene sulfide) (PEG-OES) copolymers. Assembly structural polymorphism was achieved with modification of PEG-OES topology (linear versus multiarm) and with precise, monomer-by-monomer control of OES length. Notably, all three morphologies were accessed utilizing OES oligomers with degrees of polymerization as short as three. These exceptionally small assembly forming blocks represent the first application of ethylene sulfide oligomers in supramolecular materials. While the assemblies demonstrated robust aqueous stability over time, oxidation by hydrogen peroxide progressively converted ethylene sulfide residues to increasingly hydrophilic and amorphous sulfoxides and sulfones, causing morphological changes and permanent disassembly. We utilized complementary microscopic and spectroscopic techniques to confirm this chemical stimulus-responsive behavior in self-assembled PEG-OES colloidal dispersions and physical gels. In addition to inherent stimulus-responsive behavior, fibrillar assemblies demonstrated biologically relevant molecular delivery, as confirmed by the dose-dependent activation of murine bone marrow-derived dendritic cells following fibril-mediated delivery of the immunological adjuvant monophosphoryl lipid A. In physical gels composed of either linear or multiarm PEG-OES precursors, rheologic analysis also identified mechanical stimulus-responsive shear thinning behavior. Thanks to the facile preparation, user-defined morphology, aqueous stability, carrier functionality, and stimuli-responsive behaviors of

  14. Characterization of high performance randomly segmented poly(urethane siloxane) and poly(imide siloxane) block copolymers

    NASA Astrophysics Data System (ADS)

    Doǧan, Türkan; Baydoǧan, Nilgün; Köken, Nesrin

    2016-03-01

    Poly(imide siloxane) block copolymers with the same polydimethlysiloxane(APPS) were prepared by using 4,4'-oxydianiline (ODA) and Benzofenon-3,3,4,4-tetrakarboksilik dianhydride(BTDA) to compose the polyimide hard block. APPS and BTDA composed the polysiloxane soft block. The length of polysiloxane soft blocks increased with increasing the length of polyimide hard block. Copolymerization of soft and hard segments were determined by using this method. Copolymer structures could be obtained by holding constant hard block segments and by adjusting and increasing soft block segments. Thus, more flexible randomly segmented poly(imide siloxane) block copolymers can be obtained. These composed structure as flexible and high performance copolymers were characterized by FT-IR and evaluated. The structures were tested mechanically to detect their elastic recovery property as flexible material. The characterization of the samples enabled to examine flexible substrates in order to use in solar cell, aerospace applications and microelectronic devices.

  15. Topcoat approaches for directed-assembly of copolymer films with blocks exhibiting differences in surface energy

    NASA Astrophysics Data System (ADS)

    Suh, Hyo Seon; in Lee, Jeong; Ramirez-Hernandez, Abelardo; Tada, Yasuhiko; Yoshida, Hiroshi; Wan, Lei; Ruiz, Ricardo; de Pablo, Juan; Nealey, Paul

    2013-03-01

    Fabricating patterns with feature dimensions smaller than 10 nm scale using block copolymer lithography requires the use of materials with large Flory-Huggins interaction parameters. Because such block copolymers (BCPs) typically show the large differences in surface energy between the blocks, one block (with lower surface energy) tends to segregate to the free surface of films and precludes the assembly of the desired through-film perpendicularly oriented structures. Here we describe a generalizable strategy to overcome this limitation. By coating the BCP film with an additional layer, a topcoat, thermodynamically favorable boundary conditions at the top surface of the film can be engineered for directed self-assembly. The allowable properties of the topcoats depend on the interfacial energies of the layer with the blocks of the copolymer, and the block-block interfacial energy. The strategy is demonstrated experimentally by directing the assembly of polystyrene-block-poly-2-vinylpyridine (PS- b-P2VP) films on chemically nanopatterned substrates with different topcoat materials.

  16. Reductive Decationizable Block Copolymers for Stimuli-Responsive mRNA Delivery.

    PubMed

    Nuhn, Lutz; Kaps, Leonard; Diken, Mustafa; Schuppan, Detlef; Zentel, Rudolf

    2016-06-01

    Messenger ribonucleic acids (mRNAs) are considered as promising alternatives for transient gene therapy, but to overcome their poor pharmacokinetic properties, smart carriers are required for cellular uptake and stimuli-responsive release. In this work, a synthetic concept toward reductive decationizable cationic block copolymers for mRNA complexation is introduced. By combination of RAFT block copolymerization with postpolymerization modification, cationic block copolymers are generated with disulfide-linked primary amines. They allow effective polyplex formation with negatively charged mRNA and subsequent release under reductive conditions of the cytoplasm. In first in vitro experiments with fibroblasts and macrophages, tailor-made block copolymers mediate cell-specific mRNA transfection, as quantified by polyplex uptake and mRNA-encoding gene expression. Furthermore, RAFT polymerization provides access to heterotelechelic polymers with orthogonally addressable endgroup functionalities utilized to ligate targeting units onto the polyplex-forming block copolymers. The results exemplify the broad versatility of this reductive decationizable mRNA carrier system, especially toward further advanced mRNA delivery applications. PMID:27075781

  17. The fabrication of highly ordered block copolymer micellar arrays: control of the separation distances of silicon oxide dots.

    PubMed

    Yoo, Hana; Park, Soojin

    2010-06-18

    We demonstrate the fabrication of highly ordered silicon oxide dotted arrays prepared from polydimethylsiloxane (PDMS) filled nanoporous block copolymer (BCP) films and the preparation of nanoporous, flexible Teflon or polyimide films. Polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) films were annealed in toluene vapor to enhance the lateral order of micellar arrays and were subsequently immersed in alcohol to produce nano-sized pores, which can be used as templates for filling a thin layer of PDMS. When a thin layer of PDMS was spin-coated onto nanoporous BCP films and thermally annealed at a certain temperature, the PDMS was drawn into the pores by capillary action. PDMS filled BCP templates were exposed to oxygen plasma environments in order to fabricate silicon oxide dotted arrays. By addition of PS homopolymer to PS-b-P2VP copolymer, the separation distances of micellar arrays were tuned. As-prepared silicon oxide dotted arrays were used as a hard master for fabricating nanoporous Teflon or polyimide films by spin-coating polymer precursor solutions onto silicon patterns and peeling off. This simple process enables us to fabricate highly ordered nanoporous BCP templates, silicon oxide dots, and flexible nanoporous polymer patterns with feature size of sub-20 nm over 5 cm x 5 cm. PMID:20498523

  18. RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

    PubMed Central

    Hemp, Sean T.; Smith, Adam E.; Bunyard, W. Clayton; Rubinstein, Michael H.; Long, Timothy E.

    2016-01-01

    Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels. PMID:27041771

  19. Block copolymer modified surfaces for conjugation of biomacromolecules with control of quantity and activity.

    PubMed

    Li, Xin; Wang, Mengmeng; Wang, Lei; Shi, Xiujuan; Xu, Yajun; Song, Bo; Chen, Hong

    2013-01-29

    Polymer brush layers based on block copolymers of poly(oligo(ethylene glycol) methacrylate) (POEGMA) and poly(glycidyl methacrylate) (PGMA) were formed on silicon wafers by activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). Different types of biomolecule can be conjugated to these brush layers by reaction of PGMA epoxide groups with amino groups in the biomolecule, while POEGMA, which resists nonspecific protein adsorption, provides an antifouling environment. Surfaces were characterized by water contact angle, ellipsometry, and Fourier transform infrared spectroscopy (FTIR) to confirm the modification reactions. Phase segregation of the copolymer blocks in the layers was observed by AFM. The effect of surface properties on protein conjugation was investigated using radiolabeling methods. It was shown that surfaces with POEGMA layers were protein resistant, while the quantity of protein conjugated to the diblock copolymer modified surfaces increased with increasing PGMA layer thickness. The activity of lysozyme conjugated on the surface could also be controlled by varying the thickness of the copolymer layer. When biotin was conjugated to the block copolymer grafts, the surface remained resistant to nonspecific protein adsorption but showed specific binding of avidin. These properties, that is, well-controlled quantity and activity of conjugated biomolecules and specificity of interaction with target biomolecules may be exploited for the improvement of signal-to-noise ratio in sensor applications. More generally, such surfaces may be useful as biological recognition elements of high specificity for functional biomaterials. PMID:23265296

  20. Effect of Macromolecular Architecture on the Morphology of Polystyrene Polyisoprene Block Copolymers

    SciTech Connect

    Kumar, Rajeev; Goswami, Monojoy; Mays, Jimmy; Sides, Scott; Sumpter, Bobby G; Dadmun, Mark D; Dyer, Caleb W; Driva, Paraskevi; Chen, Jihua

    2013-01-01

    The impact of block connectivity on the morphologies of four block copolymers of varying architecture containing polystyrene (PS) and polyisoprene (PI) has been studied. The volume fraction of PS and molecular weight are held constant while varying the architecture from a linear PS-PI diblock copolymer to three different miktoarm star architectures: PS2PI, PSPI2, and PS2PI2. Morphologies of the PS2PI and PSPI2 miktoarm stars are different from those observed for the linear copolymer and dependent on the connectivity of the copolymer blocks. The change in morphology with connectivity indicates that combining two chains at a junction point leads to chain crowding, where subsequent excluded volume effects drive the change in morphology for each sample. The PS2PI2 miktoarm star exhibits the same morphology as the linear diblock but with a reduction in the size of the domains. The extent of the decrease in domain size indicates that chain stretching impacts the formation of this morphology. Experimentally observed morphologies for different chain architectures are generally consistent with three-dimensional self-consistent field theory simulations, taking into account conformational asymmetry and experimental uncertainty in the copolymer composition. Furthermore, these results generally agree with analytical theory predictions that account for architectural and conformational asymmetry.

  1. Block copolymer alignment by shear induced during solvent vapor annealing with a crosslinked elastomer capping layer

    NASA Astrophysics Data System (ADS)

    Vogt, Bryan

    2014-03-01

    The long range alignment of block copolymers (BCPs) is generally accomplished through application of a gradient shear force or by topographical or chemical cues patterned into the substrate. These techniques require lithographic patterning, specialty substrates or custom built equipment to achieve the alignment, which limits the broad academic application of aligned BCPs. One technique to improve the large range ordering of BCPs is solvent vapor annealing (SVA), which exposes the BCP film to a controlled atmosphere of solvent vapor to swell the BCP and provide significant enhancements in the chain mobility. Here, we discuss a minor modification of the SVA process; a thin piece of crosslinked poly(dimethyl siloxane) (PDMS) is placed on top of the BCP film before SVA. Exposure to organic solvent vapors causes the PDMS to swell, while the solvent also plasticizes the BCP film. Removal of the solvent induces a shear to the BCP film as the PDMS shrinks back to its initial dimensions. The shape of the PDMS cap determines the anisotropy in the stress applied on deswelling that aligns and orients the BCP domains. Polystyrene-block-polyisoprene-block-polystyrene (SIS) is utilized as a model system to illustrate how the processing parameters impact the orientation as determined by both grazing incidence small angle x-ray scattering (GISAXS) and atomic force microscopy (AFM). Quantification of the alignment by Herman's orientational parameter (S) illustrates high degree of alignment (S =0.95) is possible through appropriate selection of processing conditions. This SVA-based alignment method provides a relatively simple method to orient BCP films within general SVA processing protocols.

  2. Selective separation of similarly sized proteins with tunable nanoporous block copolymer membranes.

    PubMed

    Qiu, Xiaoyan; Yu, Haizhou; Karunakaran, Madhavan; Pradeep, Neelakanda; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2013-01-22

    An integral asymmetric membrane was fabricated in a fast and one-step process by combining the self-assembly of an amphiphilic block copolymer (PS-b-P4VP) with nonsolvent-induced phase separation. The structure was found to be composed of a thin layer of densely packed highly ordered cylindrical channels with uniform pore sizes perpendicular to the surface on top of a nonordered sponge-like layer. The as-assembled membrane obtained a water flux of more than 3200 L m(-2) h(-1) bar(-1), which was at least an order of magnitude higher than the water fluxes of commercially available membranes with comparable pore sizes, making this membrane particularly well suited to size-selective and charge-based separation of biomolecules. To test the performance of the membrane, we conducted diffusion experiments at the physiological pH of 7.4 using bovine serum albumin (BSA) and globulin-γ, two proteins with different diameters but too close in size (2-fold difference in molecular mass) to be efficiently separated via conventional dialysis membrane processes. The diffusion rate differed by a factor of 87, the highest value reported to date. We also analyzed charge-based diffusive transport and separation of two proteins of similar molecular weight (BSA and bovine hemoglobin (BHb)) through the membrane as a function of external pH. The membrane achieved a selectivity of about 10 at pH 4.7, the isoelectric point (pI) of BSA. We then positively charged the membrane to improve the separation selectivity. With the modified membrane BSA was completely blocked when the pH was 7.0, the pI of BHb, while BHb was completely blocked at pH 4.7. Our results demonstrate the potential of our asymmetric membrane to efficiently separate biological substances/pharmaceuticals in bioscience, biotechnology, and biomedicine applications. PMID:23252799

  3. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    NASA Astrophysics Data System (ADS)

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-05-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating.

  4. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    PubMed Central

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-01-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

  5. Calorimetric Study of Gradient Block-copolymers of Poly(butylacrylate) and Poly(methylmethacrylate)

    NASA Astrophysics Data System (ADS)

    Buzin, A. I.; Pyda, M.; Matyjaszewski, K.; Wunderlich, B.

    2002-03-01

    The miscibility and phase separation in the diblock (AB) and triblock (ABA) copolymers consisting of poly(butyl acrylate) (block B) and gradient copolymers of butyl acrylate and methyl methacrylate (block A) were investigated by means of conventional DSC as a function of the composition of the blocks A. In all copolymers studied, both blocks are presented by two separate glass transition temperatures. The low-temperature transition corresponds to devitrification of block B and is independent of composition and temperature is close to that of pure poly(butyl acrylate), while the higher transition corresponds to glass transition of the copolymeric block A, which decreases and broadens with increasing methylmethacrylate content in block A. The immiscible polymers are connected by chemical bonds, so that the mobilities of the phases influence each other. Shifts in the glass transition temperature and the broadening of the transitions as well as their asymmetry are discussed. --- Supported by NSF, Polymers Program, DMR-9703692, and the Div. of Mat. Sci., BES, DOE at ORNL, managed by UT-Batelle, LLC, for the U.S. Department of Energy, under contract number DOE-AC05-00OR22725.

  6. Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of ultrathin block copolymer films.

    PubMed

    Huang, Changchun; Wen, Gangyao; Li, Jingdan; Wu, Tao; Wang, Lina; Xue, Feifei; Li, Hongfei; Shi, Tongfei

    2016-09-15

    Effects of copolymer composition, film thickness, and solvent vapor annealing time on dewetting of spin-coated polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films (<20nm thick) were mainly investigated by atomic force microscopy. Surface chemical analysis of the ultrathin films annealed for different times were performed using X-ray photoelectron spectroscopy and contact angle measurement. With the annealing of acetone vapor, dewetting of the films with different thicknesses occur via the spinodal dewetting and the nucleation and growth mechanisms, respectively. The PS-b-PMMA films rupture into droplets which first coalesce into large ones to reduce the surface free energy. Then the large droplets rupture into small ones to increase the contact area between PMMA blocks and acetone molecules resulting from ultimate migration of PMMA blocks to droplet surface, which is a novel dewetting process observed in spin-coated films for the first time. PMID:27309943

  7. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    NASA Astrophysics Data System (ADS)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  8. Nanomechanical properties of solvent cast polystyrene and poly(methyl methacrylate) polymer blends and self-assembled block copolymers

    NASA Astrophysics Data System (ADS)

    Lorenzoni, Matteo; Evangelio, Laura; Nicolet, Célia; Navarro, Christophe; San Paulo, Alvaro; Rius, Gemma; Pérez-Murano, Francesc

    2015-07-01

    The nanomechanical properties of solvent-cast polymer thin films have been investigated using PeakForce™ Quantitative Nanomechanical Mapping. The samples consisted of films of polystyrene (PS) and poly(methyl methacrylate) (PMMA) obtained after the dewetting of toluene solution on a polymeric brush layer. Additionally, we have probed the mechanical properties of poly(styrene-b-methyl methacrylate) block copolymers (BCP) as randomly oriented thin films. The probed films have a critical thickness <50 nm and present features to be resolved <42 nm. The Young's modulus values obtained through several nanoindentation experiments present a good agreement with previous literature, suggesting that the PeakForce™ technique could be crucial for BCP investigations, e.g., as a predictor of the mechanical stability of the different phases.

  9. Strain-controlled fluorescence polarization in a CdSe nanoplatelet-block copolymer composite.

    PubMed

    Beaudoin, E; Abecassis, B; Constantin, D; Degrouard, J; Davidson, P

    2015-03-01

    By dispersing semi-conducting CdSe nanoplatelets within a styrene-butadiene-styrene block copolymer matrix we form homogeneous fluorescent hybrid films. Reversible orientation control of the nanoplatelets is simply achieved through stretching the film, leading to tuneable fluorescence anisotropy. Such adjustable polarization effects are useful for modulating the optical response in composite materials. PMID:25664355

  10. Self-assembly of peptoid block copolymers with tunable conformational asymmetry

    NASA Astrophysics Data System (ADS)

    Rosales, Adrianne; Zuckermann, Ronald; Segalman, Rachel

    2013-03-01

    Functional polymers such as conjugated or biological molecules have been shown to have a variety of chain conformations that affect their self-assembly. Polypeptoids are sequence-specific biomimetic polymers for which the statistical segment length can be tuned by the introduction of monomers with bulky, chiral side chains, allowing one to change the polymer conformation independent of chemical structure or molecular weight. Furthermore, sequence specificity enables the precise placement of those chiral monomers along the polymer chain. This work presents a systematic study of block copolymer self-assembly using chiral polypeptoids or their racemic analogs and poly(n-butyl acrylate). For the chiral block copolymers, SAXS measurements reveal that the change in conformational asymmetry increases the morphological domain spacing and decreases the corresponding interfacial area per chain, indicating that the chiral peptoid chains can pack more closely within the domain compared to the racemic peptoid chains. The effect on domain spacing is also probed by changing the position of the chiral monomers with respect to the block copolymer junction. These results lend insight to the design of block copolymers with secondary structure.

  11. Star block-copolymers: enzyme-inspired catalysts for oxidation of alcohols in water.

    PubMed

    Mugemana, Clément; Chen, Ba-Tian; Bukhryakov, Konstantin V; Rodionov, Valentin

    2014-07-25

    A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. PMID:24912078

  12. Multiscale Control of Hierarchical Structure in Crystalline Block Copolymer Nanoparticles Using Microfluidics.

    PubMed

    Bains, Aman; Cao, Yimeng; Moffitt, Matthew G

    2015-11-01

    Hierarchical semicrystalline block copolymer nanoparticles are produced in a segmented gas-liquid microfluidic reactor with top-down control of multiscale structural features, including nanoparticle morphologies, sizes, and internal crystallinities. Control of multiscale structure on disparate length scales by a single control variable (flow rate) enables tailoring of drug delivery nanoparticle function including release rates. PMID:26305569

  13. Effect of Electric Field Alignment on Morphology and Ionic Conductivity of Polymerized Ionic Liquid Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Nykaza, Jacob; Elabd, Yossef A.; Winey, Karen I.

    2014-03-01

    Polymerized ionic liquid (PIL) block copolymers are appealing for numerous electrochemical applications, including solid polymer electrolyte membranes for batteries and anion exchange membranes for fuel cells. The extent to which the reduced segmental motion caused by the non-conducting polymer segments and grain boundaries between block copolymer microdomains are detrimental to ionic conductivity is unknown. Increased long-range morphological order and connectivity of PIL microdomains are key to understanding the ion transport mechanism and may improve the ionic conductivity of PIL block copolymers. The effect of electric field on the morphology and ionic conductivity of poly(styrene- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-bis(trifluoromethanesulfonyl)imide)) (PS- b-PMEBIm-TFSI) will be discussed as a function of microdomain orientation. Electric field is used to increase the perpendicular orientation of ion-conducting pathways with respect to the electrodes. The morphology and ionic conductivity were characterized by small-angle X-ray scattering and electrochemical impedance spectroscopy, respectively. The ionic conductivity of unoriented and oriented block copolymers will be compared to the PIL homopolymer, PMEBIm-TFSI, using the Sax and Ottino model.

  14. Vertically Aligned Nanoplate Particles Directed by Block Copolymer Domains for Anisotropic Properties

    NASA Astrophysics Data System (ADS)

    Krook, Nadia; Meth, Jeffrey; Murray, Christopher; Riggleman, Robert; Composto, Russell

    During common processing methods, anisotropic fillers in polymer nanocomposites align in the direction of flow, parallel to the surfaces, thus enhancing properties in the plane of the substrate. This research aims to create thin film nanocomposites with perpendicularly aligned anisotropic particles to improve properties in the out-of-plane direction. The demonstrated work explores vertical orientation of rare-earth fluoride nanoplates in lamellar-forming poly(styrene- b-methyl methacrylate) to establish a platform that controls the alignment of any planar particle. Currently, gadolinium fluoride (GdF3) rhombus nanoplates with the longest and shortest diagonal dimensions of ~30 nm and ~25 nm, respectively, have been specially synthesized with the potential to intercalate the block copolymer (BCP) domains. By employing a ternary brush blend layer to neutralize silicon substrates to both BCP domains, vertical lamellae orientation has been enabled with an optimum film thickness of ~110 nm. The GdF3 surfaces are chemically modified to drive the plates to a specific BCP domain. After surface modification, the dispersion of GdF3 in homopolymer will first be shown followed by morphology results from integrating GdF3 into the BCP using scanning and transmission electron microscopy.

  15. Directed Assembly of Block Copolymer Ordering on Rough and Patterned Flexible Substrates

    NASA Astrophysics Data System (ADS)

    Hayirlioglu, Arzu; Kulkarni, Manish; Karim, Alamgir

    2013-03-01

    Directed self-assembly of block copolymer (BCP) thin film on flexible substrates has potential in fabrication of flexible electronic devices due to its nanometer scale pattern formation capability. We studied the BCP ordering properties of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) films on a flexible substrate, where the PS-b-PMMA films are initially coated on a smooth poly(dimethylsiloxane) (PDMS) substrate, whose surface energy (SE) was tuned between (20-69) mJ/m2 by UV-ozone (UVO) exposure. This range of SE allows for controlled wettability and orientation of the BCP overlayer. Further, we replicated different patterned media and observed perpendicular lamellar BCP orientation and parallel cylindrical BCP orientation on patterned flexible PDMS in the wetting SE regime. Rough surface structures created by silica xerogels were replicated on PDMS. RMS roughness of the xerogels is tuned by controlling sol-gel catalyst concentration and aging time. Effect of the aspect ratio of the rough PDMS substrates on the orientation of BCP films was studied. Surface morphology of the BCP films was studied by optical microscopy and Atomic Force Microscope (AFM), while orientation of the film's interior was studied using Grazing-Incidence Small Angle X-ray Scattering (GISAXS)

  16. Ultrasmooth, Polydopamine Modified Surfaces for Block Copolymer Nanopatterning on Inert and Flexible Substrates

    NASA Astrophysics Data System (ADS)

    Katsumata, Reika; Cho, Joon Hee; Zhou, Sunshine; Kim, Chae Bin; Dulaney, Austin; Janes, Dustin; Ellison, Christopher

    Nature has engineered universal, catechol-containing adhesives that can be synthetically mimicked in the form of polydopamine (PDA). We exploited PDA to enable block copolymer (BCP) nanopatterning on a variety of soft material surfaces in a way that can potentially be applied to flexible electrical devices. Applying BCP nanopatterning to soft substrates is challenging because soft substrates are often chemically inert and possess incompatible low surface energies. In this study, we exploited PDA to enable the formation of BCP nanopatterns on a variety of surfaces such as Teflon, poly(ethylene terephthalate) (PET), and Kapton. While previous studies produced a PDA coating layer too rough for BCP nanopatterning, we succeeded in fabricating conformal and ultra-smooth surfaces of PDA by engineering the PDA coating process and post-sonication procedure. This chemically functionalized, biomimetic thin film (3 nm thick) served as a reactive platform for subsequently grafting a surface treatment to perpendicularly orient a lamellae-forming BCP layer. Furthermore, we demonstrated that a perfectly nanopatterned PDA-PET substrate can be bent without distorting or damaging the nanopattern in conditions that far exceeds typical bending curvatures in roll-to-roll manufacturing.

  17. Nonlinear rheological behavior associated with structural transitions in block copolymer solutions via nonequilibrium molecular dynamics.

    PubMed

    Rychkov, Igor; Yoshikawa, Kenichi

    2004-02-15

    The nonequilibrium molecular dynamics computer simulation method was used to study microsegregated block copolymer systems in a selective solvent under a shear flow field. Two polymer concentrations were considered, 0.3 and 0.4, corresponding to the body centered cubic spherical and hexagonal cylindrical zero-shear phases, respectively. As the shear rate increased, both systems exhibited two-stage shear thinning, a peak in the scalar pressure, and normal stress differences. Microscopic connections were investigated by calculating the gyration and bond orientation tensors and the interaction energies per particle. At high shear rates, polymer chains elongate and orient along the direction of shear, and this is accompanied by the breaking-up of domains. The structure-rheology relation was discussed with regard to the morphological changes reported in our last study for the same systems. In particular, the structurally relevant critical values of the shear rate were found to delimit different behaviors of the shear rate-dependencies obtained in this work. PMID:15268506

  18. Resistive switching in high-density nanodevices fabricated by block copolymer self-assembly.

    PubMed

    Frascaroli, Jacopo; Brivio, Stefano; Ferrarese Lupi, Federico; Seguini, Gabriele; Boarino, Luca; Perego, Michele; Spiga, Sabina

    2015-03-24

    Bipolar resistive switching memories based on metal oxides offer a great potential in terms of simple process integration, memory performance, and scalability. In view of ultrahigh density memory applications, a reduced device size is not the only requirement, as the distance between different devices is a key parameter. By exploiting a bottom-up fabrication approach based on block copolymer self-assembling, we obtained the parallel production of bilayer Pt/Ti top electrodes arranged in periodic arrays over the HfO2/TiN surface, building memory devices with a diameter of 28 nm and a density of 5 × 10(10) devices/cm(2). For an electrical characterization, the sharp conducting tip of an atomic force microscope was adopted for a selective addressing of the nanodevices. The presence of devices showing high conductance in the initial state was directly connected with scattered leakage current paths in the bare oxide film, while with bipolar voltage operations we obtained reversible set/reset transitions irrespective of the conductance variability in the initial state. Finally, we disclosed a scalability limit for ultrahigh density memory arrays based on continuous HfO2 thin films, in which a cross-talk between distinct nanodevices can occur during both set and reset transitions. PMID:25743480

  19. Orientational control of block copolymer microdomains by sub-tesla magnetic fields

    NASA Astrophysics Data System (ADS)

    Gopinadhan, Manesh; Choo, Youngwoo; Feng, Xunda; Kawabata, Kohsuke; di, Xiaojun; Osuji, Chinedum

    Magnetic fields offer a versatile approach to controlling the orientation of block copolymer (BCP) microdomains during self-assembly. To date however, such control has required the imposition of large magnetic fields (>3T), necessitating the use of complex magnet systems - either superconducting or very large conventional resistive magnets. Here we demonstrate the ability to direct BCP self-assembly using considerably smaller fields (<1T) which are accessible using simple rare-earth permanent magnets. The low field alignment is enabled by the presence of small quantities of mesogenic species that are blended into, and co-assemble with the liquid crystalline (LC) mesophase of the side-chain LC BCP under study. In situ SAXS experiments reveal a pronounced dependence of the critical alignment field strength on the stoichiometry of the blend, and the ability to generate aligned microdomains with orientational distribution coefficients exceeding 0.95 at sub-1 T fields for appropriate stoichiometries. The alignment response overall can be rationalized in terms of increased mobility and grain size due to the presence of the mesogenic additive. We use a permanent magnet to fabricate films with aligned nanopores, and the utility of this approach to generate complex BCP microdomain patterns in thin films by local field screening are highlighted. NSF DMR-1410568 and DMR-0847534.

  20. Asymmetrical Self-assembly From Fluorinated and Sulfonated Block Copolymers in Aqueous Media

    SciTech Connect

    Wang, Xiaojun; Hong, Kunlun; Baskaran, Durairaj; Goswami, Monojoy; Sumpter, Bobby G; Mays, Jimmy

    2011-01-01

    Block copolymers of fluorinated isoprene and partially sulfonated styrene form novel tapered rods and ribbon-like micelles in aqueous media due to a distribution of sulfonation sites and a large Flory-Huggins interaction parameter. A combination of microscopy, light scattering, and simulation demonstrates the presence of these unique nanostructures. This study sheds light on the micellization behavior of amphiphilic block polymers by revealing a new mechanism of self-assembly.

  1. Assembly of Double-Hydrophilic Block Copolymers Triggered by Gadolinium Ions: New Colloidal MRI Contrast Agents.

    PubMed

    Frangville, Camille; Li, Yichen; Billotey, Claire; Talham, Daniel R; Taleb, Jacqueline; Roux, Patrick; Marty, Jean-Daniel; Mingotaud, Christophe

    2016-07-13

    Mixing double-hydrophilic block copolymers containing a poly(acrylic acid) block with gadolinium ions in water leads to the spontaneous formation of polymeric nanoparticles. With an average diameter near 20 nm, the nanoparticles are exceptionally stable, even after dilution and over a large range of pH and ionic strength. High magnetic relaxivities were measured in vitro for these biocompatible colloids, and in vivo magnetic resonance imaging on rats demonstrates the potential utility of such polymeric assemblies. PMID:27224089

  2. Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions.

    PubMed

    Zheng, Lingfei; Wu, Jianqi; Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

    2016-07-01

    The phase behavior of symmetric ABC triple-hydrophilic triblock copolymers in concentrated aqueous solutions is investigated using a simulated annealing technique. Two typical cases, in which the hydrophilicity of the middle B-block is either stronger or weaker than that of the end A- and C-blocks, are studied. In these two cases, a variety of phase diagrams are constructed as a function of the volume fraction of the B-block and the copolymer concentration ([Formula: see text] for both non-frustrated and frustrated copolymers. Structures, such as two-color alternatingly packed cylinders or gyroid, and lamellae-in-lamellae etc. that do not occur in the melt system, are obtained in solutions. Rich phase transition sequences, especially re-entrant phase transitions involving complex continuous networks of alternating gyroid and alternating diamond are observed for a given copolymer with decreasing [Formula: see text] . The difference in hydrophilicity among different blocks can result in inhomogeneous distribution of solvent molecules in the morphology, and with the decrease of [Formula: see text] , the distribution of solvent molecules presents a non-monotonic variation. This results in a non-monotonic variation of the effective volume fraction of each domain with the decrease of [Formula: see text] , which induces the re-entrant phase transitions. The presence of a good solvent for all the blocks can cause changes in the effective segregation strengths between different blocks and also in chain conformations, hence can alter the bulk phases and results in the occurrence of new structures and phase transitions. Especially, structures having A-C interfaces or A-C mixed domains can be obtained even in the non-frustrated copolymer systems, and structures obtained in the frustrated systems may be similar to those obtained in the non-frustrated systems. The window of the alternating gyroid structures may occupy a large part of the phase diagram for non

  3. Controlling Miscibility in Polyethylene-Polynorbornene Block Copolymers via Side-Group Chemistry

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Block copolymers containing a crystallizable block, such as polyethylene (PE), and an amorphous block with high glass transition temperature (Tg) are an interesting class of materials since the rigid glassy block can improve the mechanical response of the article under strain by reinforcing the crystal fold surface. However, to prepare an easily processable PE-containing block copolymer it is necessary to avoid microphase separation in the melt by selection of amorphous blocks with weak repulsive interactions against PE (low Flory interaction parameter χ or interaction energy density X) . Most such low- χ polymers are chemically similar to PE, such as copolymers of ethylene and a small amount of an α-olefin, and therefore exhibit similarly low glass transition temperatures. This work investigates a series of low- and high-Tg polymers based on substituted norbornene monomers, polymerized via ring-opening metathesis polymerization (ROMP). Hydrogenated polynorbornene derivatives possess a wide range of glass transition temperatures, and miscibility with PE can be readily tuned by the choice of substituents on the monomers (e.g. aromatic vs. aliphatic groups). Two species investigated, hydrogenated poly(cyclohexyl norbornene) and hydrogenated poly(norbornyl norbornene), have high Tg and also remain miscible with polyethylene to high molecular weight. Furthermore, we develop a set of mixing rules to qualitatively predict the solubility behavior of substituted ROMP polynorbornenes as a function of their side-groups.

  4. Antimicrobial films obtained from latex particles functionalized with quaternized block copolymers.

    PubMed

    Alvarez-Paino, Marta; Juan-Rodríguez, Rafael; Cuervo-Rodríguez, Rocío; Tejero, Rubén; López, Daniel; López-Fabal, Fátima; Gómez-Garcés, José L; Muñoz-Bonilla, Alexandra; Fernández-García, Marta

    2016-04-01

    New amphiphilic block copolymers with antimicrobial properties were obtained by atom transfer radical polymerization (ATRP) and copper catalyzed cycloaddition following two approaches, a simultaneous strategy or a two-step synthesis, which were proven to be very effective methods. These copolymers were subsequently quaternized using two alkyl chains, methyl and butyl, to amplify their antimicrobial properties and to investigate the effect of alkyl length. Antimicrobial experiments in solution were performed with three types of bacteria, two gram-positive and one gram-negative, and a fungus. Those copolymers quaternized with methyl iodide showed better selectivities on gram-positive bacteria, Staphylococcus aureus and Staphylococcus epidermidis, against red blood cells, demonstrating the importance of the quaternizing agent chosen. Once the solution studies were performed, we prepared poly(butyl methacrylate) latex particles functionalized with the antimicrobial copolymers by emulsion polymerization of butyl methacrylate using such copolymers as surfactants. The characterization by various techniques served to test their effectiveness as surfactants. Finally, films were prepared from these emulsions, and their antimicrobial activity was studied against the gram-positive bacteria. The results indicate that the antimicrobial efficiency of the films depends not only on the copolymer activity but also on other factors such as the surface segregation of the antimicrobial agent to the interface. PMID:26741269

  5. Characterization of a Poly(styrene-block-methylacrylate-random-octadecylacrylate-block-styrene) Shape Memory ABA Triblock Copolymer

    NASA Astrophysics Data System (ADS)

    Fei, Pengzhan; Cavicchi, Kevin

    2011-03-01

    A new ABA triblock copolymer of poly(styrene-block- methylacrylate-random-octadecylacrylate-block-styrene) (PS-b- PMA-r-PODA-b-PS) was synthesized by reversible addition fragmentation chain transfer polymerization. The triblock copolymer can generate a three-dimensional, physically crosslinked network by self-assembly, where the glassy PS domains physically crosslink the midblock chains. The side chain crystallization of the polyoctadecylacrylare (PODA) side chain generates a second reversible network enabling shape memory properties. Shape memory tests by uniaxial deformation and recovery of molded dog-bone shape samples demonstrate that shape fixities above 96% and shape recoveries above 98% were obtained for extensional strains up to 300%. An outstanding advantage of this shape memory material is that it can be very easily shaped and remolded by elevating the temperature to 140circ; C, and after remolding the initial shape memory properties are totally recovered by eliminating the defects introduced by the previous deformation cycling.

  6. Theory for dynamical self arrest and gelation in microemulsions and the block copolymer systems

    SciTech Connect

    Wu, Sangwook

    2005-05-01

    The main purpose of this work is to investigate the glassy behavior of microemulsions and block copolymers. The origin of glassy behavior in microemulsions and block copolymers is frustration due to a competition between short-range interaction and long range interaction. According to the charge frustrated Ising model, the competition between ferromagnetic interaction and antiferromagnetic interaction is the origin of frustration in microemulsions. The competition between entropic effects and stoichiometric constraints responsible for the formation of micelles in microemulsions can lead to the emergence of a self generated glassy behavior in these systems. In the block copolymer, the competition between the repulsive short range interaction between monomers in polymer chains and the long range interaction by chemical bonds can lead to the emergence of a self generated glassy behavior. The criteria for the fluctuation induced first order transition and our microemulsion and block copolymer glasses are essentially the same. Both are a consequence of the large phase space of low energy excitations (14) (62) (all states with momenta q which fulfill |q| = q{sub m}) and are of at the most a moderate supercooling of the liquid state is required. This is strongly supported by the observation in Ref. (14) that the metastable states which are first to appear at a fluctuation induced first order transition are the ones build by a superposition of large amplitude waves of wavenumber q{sub m}, but with random orientations and phases, i.e. just the ones which form the metastable states of our microemulsion and block copolymer glass. (38)

  7. Large-area, ordered hexagonal arrays of nanoscale holes or dots from block copolymer templates

    SciTech Connect

    Vedrine, Josee; Hong, Young-Rae; Marencic, Andrew P.; Register, Richard A.; Adamson, Douglas H.; Chaikin, Paul M.

    2007-10-01

    Hexagonal arrays of nanoscale holes or metal dots (25 nm in diameter and 39 nm in period), with orientational order extending over the entire square-centimeter array area, were fabricated on unpatterned silicon wafer substrates using a shear-aligned sphere-forming diblock copolymer template. Since two or more layers of spherical nanodomains are required to achieve alignment in the block copolymer film, but pattern transfer requires a single layer, a multistep etching process was developed, whereby the top layer of a shear-aligned bilayer was evenly removed, leaving the ordered bottom layer as the fabrication template for hole and dot arrays free from grain boundaries.

  8. Reversible Micro- and Nano- Phase Programming of Anthraquinone Thermochromism Using Blended Block Copolymers.

    PubMed

    Zhang, Yumiao; Lovell, Jonathan F

    2015-12-22

    Here, we present an approach to generate materials with programmable thermochromic transition temperatures (TTTs), based on the reversible microcrystallization of anthraquinone dyes with the assistance of blended Pluronic block copolymers. At temperatures above block copolymer critical micellization temperature (CMT), hydrophobic anthraquinone dyes, including Sudan blue II, were dispersed in copolymer micelles, whereas at lower temperature, the dyes formed microcrystals driven by dye-dye and dye-Pluronic molecular interactions. The crystallization process altered the optical properties of the dye with bathochromatic shifts detectable by eye and the thermochromic process was fully reversible. Not only could Pluronic reversibly incorporate the anthraquinone dyes into micelles at elevated temperatures, but it also modulated the crystallization process and resulting morphology of microcrystals via tuning the molecular interactions when the temperature was lowered. Crystal melting transition points (and TTTs) were in agreement with the CMTs, dem