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

Description: 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.
Date: November 27, 2006
Creator: Virgili, Justin M.; Tao, Yuefei; Kortright, Jeffrey B.; Balsara,Nitash P. & Segalman, Rachel A.
Partner: UNT Libraries Government Documents Department

Final Report: Grant DE-FG02-05ER15682. Simulation of Complex Microphase Formation in Pure and Nanoparticle-filled Diblock Copolymers

Description: The goal of this project was to use molecular simulation to quantify the impact of additives on the onset and structure of bicontinuous phases in linear diblock copolymers (DBC). The focus was on understanding how additives with selective affinity for a given block will distribute and perturb the structure of complex bicontinuous phases (like gyroid, double diamond, and plumbers nightmare whose minority component block forms two interweaving 3D networks) in DBCs; it was hypothesized that a suitable choice of additive type, size, affinity, and concentration may suppress or stabilize a particular bicontinuous phase. The ultimate goal in this line of investigation is to elucidate the rational design of the optimal additive for which the composition range of stability of a particular bicontinuous phase is maximized. Ours are the first published simulation studies to report on the formation of the gyroid phase in DBC melts and of other bicontinuous phases in DBC-modified by homopolymer. The following tasks were carried out: (i) simulation of bicontinuous phases of pure DBCs via both on-lattice Monte Carlo simulations and continuum-space Monte Carlo and molecular dynamics simulations, (ii) determination of the effect of selective additives (homopolymer) of different sizes on such bicontinuous phases, and (iii) development of novel Monte Carlo methods to map out reliable phase diagrams and improve ergodic sampling; in particular, optimized expanded-ensemble techniques for measuring free-energies and for chemical potential equilibration.
Date: November 18, 2009
Creator: Escobedo, Fernando A.
Partner: UNT Libraries Government Documents Department

Nanopatterned ferroelectrics for ultrahigh density rad-hard nonvolatile memories.

Description: Radiation hard nonvolatile random access memory (NVRAM) is a crucial component for DOE and DOD surveillance and defense applications. NVRAMs based upon ferroelectric materials (also known as FERAMs) are proven to work in radiation-rich environments and inherently require less power than many other NVRAM technologies. However, fabrication and integration challenges have led to state-of-the-art FERAMs still being fabricated using a 130nm process while competing phase-change memory (PRAM) has been demonstrated with a 20nm process. Use of block copolymer lithography is a promising approach to patterning at the sub-32nm scale, but is currently limited to self-assembly directly on Si or SiO{sub 2} layers. Successful integration of ferroelectrics with discrete and addressable features of {approx}15-20nm would represent a 100-fold improvement in areal memory density and would enable more highly integrated electronic devices required for systems advances. Towards this end, we have developed a technique that allows us to carry out block copolymer self-assembly directly on a huge variety of different materials and have investigated the fabrication, integration, and characterization of electroceramic materials - primarily focused on solution-derived ferroelectrics - with discrete features of {approx}20nm and below. Significant challenges remain before such techniques will be capable of fabricating fully integrated NVRAM devices, but the tools developed for this effort are already finding broader use. This report introduces the nanopatterned NVRAM device concept as a mechanism for motivating the subsequent studies, but the bulk of the document will focus on the platform and technology development.
Date: September 1, 2010
Creator: Brennecka, Geoffrey L.; Stevens, Jeffrey; Scrymgeour, David; Gin, Aaron V. & Tuttle, Bruce Andrew
Partner: UNT Libraries Government Documents Department

MaterialsSemicrystallineCopolyamidesBased on the Renewable Monomer, 1,9-Nonane Diamine

Description: The conclusions of the presentation are: (1) Confirmed Isomorphism; (2) Reproduced Sigmoidal Relationship Between Melting Temperature and Composition; (3) Tg Increased with Increasing 9T Content; (4) Thermal Stability Increased with Increasing 9T Content; (5) Crystallization Rate Increased Dramatically at 9T Contents Above 50 Mole %; and (6) Copolymers Possessing a 9T Content Exceeding 50 Mole % 9T Possess Very Desirable Thermal Properties That Rival Nylon 6,6.
Date: December 16, 2010
Creator: Kugal, Alex; He, Jie; Bahr, James; Nasrullah, Mohammed & Chisholm, Bret
Partner: UNT Libraries Government Documents Department

Effect on Performance of Composition of Li-Ion Carbon Anodes Derived from PMAN/DVB Copolymers

Description: The effects on electrochemical performance of the nitrogen content of disordered carbons derived from polymethacryonitrile (PMAN)-divinylbenzene (DVB) copolymers were examined in galvanostatic cycling tests between 2 V and 0.01 V vs. Li/Li+ in lM LiPF<sub>6</sub>/ethylene carbonate (EC)-dimethyl carbonate (DMC). The first-cycle reversible capacities and coulombic efficiencies increased with increase in the level of nitrogen for samples prepared at 700&deg;C. However, the degree of fade also increased. Similar tests were performed on materials that were additionally heated at 1,000&deg; and 1,300&deg;C for five hours. Loss of nitrogen, oxygen, and hydrogen occurred under these conditions, with none remaining at the highest temperature in all cases but one. The pyrolysis temperature dominated the electrochemical performance for these samples, with lower reversible and irreversible capacities for the first intercalation cycle as the pyrolysis temperature was increased. Fade was reduced and coulombic efficiencies also improved with increase in temperate. The large irreversible capacities and high fade of these materials makes them unsuitable for use in Li-ion cells.
Date: May 14, 1999
Creator: Even, William R. & Guidotti, Ronald A.
Partner: UNT Libraries Government Documents Department

Confinement of block copolymers

Description: 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.
Date: December 31, 1995
Partner: UNT Libraries Government Documents Department

Nanostructured block copolymers.

Description: Block copolymers are well known to undergo micro-phase separation. Typical domain sizes range from a few to about 100 nanometers. With use of OPV{sub n-}PEG{sub m} diblock copolymers, long nanofiber, short nanorod, and lamella morphologies have been observed. OPV is oligo(phenylenevinylene) and PEG is poly(ethyleneglycol). The OPV segment is photoluminescent as well as electroluminescent. The micrometer long OPV{sub 13-}PEG{sub 45} nanofiber consists of OPV{sub 13} inner core with radius of 5.2 nm, and PEG{sub 45} outer shell with overall fiber radius of 7.9 nm. The nanorod has similar core-shell composition but with much shorter length of {approx}100 nm. Lamella morphology consists of alternating OPV and PEG layers. The structural characterization and physical properties of these nanostructured materials and their implication are summarized.
Date: July 9, 2002
Creator: Wang, H. H.; Wang, H.; Yu, L.; Han, C. Y.; Csencsits, R.; Willing, G. A. et al.
Partner: UNT Libraries Government Documents Department

Responsive Copolymers for Enhanced Petroleum Recovery

Description: The objectives of this work was to: (1) synthesize responsive, amphiphilic systems; (2) characterize molecular structure and solution behavior; (3) measure rheological properties of the aqueous fluids including behavior in fixed geometry flow profiles and beds; and (4) to tailor polymer compositions for in situ rheology control under simulated reservoir conditions.
Date: February 27, 2002
Creator: McCormick, Charles & Hester, Roger
Partner: UNT Libraries Government Documents Department

"Smart" Multifunctional Polymers for Enhanced Oil Recovery

Description: Herein we report the synthesis and solution characterization of a novel series of AB diblock copolymers with neutral, water-soluble A blocks comprised of N,N-dimethylacrylamide (DMA) and pH-responsive B blocks of N,N-dimethylvinylbenzylamine (DMVBA). To our knowledge, this represents the first example of an acrylamido-styrenic block copolymer prepared directly in homogeneous aqueous solution. The best blocking order (using polyDMA as a macro-CTA) was shown to yield well-defined block copolymers with minimal homopolymer impurity. Reversible aggregation of these block copolymers in aqueous media was studied by {sup 1}H NMR spectroscopy and dynamic light scattering. Finally, an example of core-crosslinked micelles was demonstrated by the addition of a difunctional crosslinking agent to a micellar solution of the parent block copolymer. Our ability to form micelles directly in water that are responsive to pH represents an important milestone in developing ''smart'' multifunctional polymers that have potential for oil mobilization in Enhanced Oil Recovery Processes.
Date: October 15, 2005
Creator: McCormick, Charles & Lowe, Andrew
Partner: UNT Libraries Government Documents Department

Nanoscale Structural Engineering of Ferroelectric Polymers. Final Report for July 2001-June 2005

Description: This final report describes the interaction between multilavered films of polymer ferroelectrics, in our case the copolymers of PVDF formed with TrFE. Langmuir Blodgett deposition of these films allows the deposition of thin, uniform, highly crystalline films. Two type of multilayer stacks are made and characterized. The first consists of multilayer stacks of the copolymer films with 2 different TrFE contents-50% and 20%. By varying the period of the multilayer stacks we see evidence of interaction at short length scales, evidenced in the thermodynamic transition temperatures of the multilayer films. The second set consists of a P(VDF - TrFE) film sandwiched between two Cobalt electrodes. In these we see evidence of a large magnetoelectric coupling.
Date: December 1, 2005
Creator: Adenwalla, S.
Partner: UNT Libraries Government Documents Department

Bridging properties of multiblock copolymers.

Description: Using self-consistent field theory, we attempt to elucidate the links between microscopically determined properties, such as the bridging fraction of chains, and mechanical properties of multiblock copolymer materials. We determine morphological aspects such as period and interfacial width and calculate the bridging fractions, and compare with experimental data .
Date: January 1, 2003
Creator: Rasmussen, K. O. (Kim O.); Kober, E. M. (Edward M.); Lookman, T. (Turab) & Saxena, A. B. (Avadh B.)
Partner: UNT Libraries Government Documents Department

Biomimetic Nanocomposites of Calcium Phosphate and Self-Assembling Triblock and Pentablock Copolymers

Description: In an effort to mimic the growth of natural bone, self-assembling, micelle and gel-forming copolymers were used as a template for calcium phosphate precipitation. Because of the cationic characteristics imparted by PDEAEM end group additions to commercially available Pluronic{reg_sign} Fl27, a direct ionic attraction mechanism was utilized and a polymer-brushite nanocomposite spheres were produced. Brushite coated spherical micelles with diameters of {approx}40 nm, and agglomerates of these particles (on the order of 0.5 {mu}m) were obtained. Thickness and durability of the calcium phosphate coating, and the extent of agglomeration were studied. The coating has been shown to be robust enough to retain its integrity even below polymer critical micelle concentration and/or temperature. Calcium phosphate-polymer gel nanocomposites were also prepared. Gel samples appeared as a single phase network of agglomerated spherical micelles, and had a final calcium phosphate concentration of up to 15 wt%. Analysis with x-ray diffraction and NMR indicated a disordered brushite phase with the phosphate groups linking inorganic phase to the polymer.
Date: August 9, 2006
Creator: Enlow, Drew Lenzen
Partner: UNT Libraries Government Documents Department

The in-situ generation of silica reinforcement in modified polydimethylsiloxane elastomers

Description: Structure and properties of a series of modified polydimethylsiloxane (PDMS) elastomers reinforced by {ital in situ} generated silic particles were investigated. The PDMS elastomer was modified by systematically varying the molecular weight between reactive groups incorporated into the backbone. Tetraethoxysilane (TEOS) and partial hydrolyzate of TEOS were used to generate silic particles. Chemistry and phase structure of the materials were investigated by {sup 29}Si magic angle spinning nuclear magnetic resonance spectroscopy and swelling experiments.
Date: June 1, 1996
Creator: Prabakar, S; Bates, S.E.; Black, E.P. & Ulibarri, T.A.
Partner: UNT Libraries Government Documents Department

Aerosol-Assisted Self-Assembly of Mesostructured Spherical Nanoparticles

Description: Nanostructured particles exhibiting well-defined pore sizes and pore connectivities (1-, 2-, or 3-dimensional) are of interest for catalysis, chromatography, controlled release, low dielectric constant fillers, and custom-designed pigments and optical hosts. During the last several years considerable progress has been made on controlling the macroscopic forms of mesoporous silicas prepared by surfactant and block copolymer liquid crystalline templating procedures. Typically interfacial phenomena are used to control the macroscopic form (particles, fibers, or films), while self-assembly of amphiphilic surfactants or polymers is used to control the mesostructure. To date, although a variety of spherical or nearly-spherical particles have been prepared, their extent of order is limited as is the range of attainable mesostructures. They report a rapid, aerosol process that results in solid, completely ordered spherical particles with stable hexagonal, cubic, or vesicular mesostructures. The process relies on evaporation-induced interfacial self-assembly (EISA) confined to a spherical aerosol droplet. The process is simple and generalizable to a variety of materials combinations. Additionally, it can be modified to provide the first aerosol route to the formation of ordered mesostructured films.
Date: March 23, 1999
Creator: Brinker, C.J.; Fan,; H.; Lu, Y.; Rieker, T.; Stump, A. et al.
Partner: UNT Libraries Government Documents Department

Microphase separation in a model graft copolymer

Description: We present a preliminary overview of our work on a series of graft copolymers having poly(ethyl acrylate) backbones with pendant chains of polystyrene (PS). The copolymer system appeared to be in the strong segregation limit and exhibited evidence of ordered structures. The morphology of these structures can apparently be very different from what would be expected. For instance, we observed a lamellar structure in a material containing 28 wt.% PS grafts. Samples under uniaxial strain showed either conventional (i.e., affine deformation) and anomalous ({open_quotes}butterfly{close_quotes} isointensity patterns) behavior in small-angle neutron scattering.
Date: October 1, 1993
Creator: Dozier, W.D.; Thiyagarajan, P. & Peiffer, D.G.
Partner: UNT Libraries Government Documents Department

Engineered monodisperse mesoporous materials

Description: Porous materials technology has developed products with a wide variety of pore sizes ranging from 1 angstrom to 100`s of microns and beyond. Beyond 15{angstrom} it becomes difficult to obtain well ordered, monodisperse pores. In this report the authors describe efforts in making novel porous material having monodisperse, controllable pore sizes spanning the mesoporous range (20--500 {angstrom}). They set forth to achieve this by using unique properties associated with block copolymers--two linear homopolymers attached at their ends. Block copolymers phase separate into monodisperse mesophases. They desired to selectively remove one of the phases and leave the other behind, giving the uniform monodisperse pores. To try to achieve this the authors used ring-opening metathesis polymerization to make the block copolymers. They synthesized a wide variety of monomers and surveyed their polymers by TGA, with the idea that one phase could be made thermally labile while the other phase would be thermally stable. In the precipitated and sol-gel processed materials, they determined by porosimetry measurements that micropores, mesopores, and macropores were created. In the film processed sample there was not much porosity present. They moved to a new system that required much lower thermal treatments to thermally remove over 90% of the labile phase. Film casting followed by thermal treatment and solvent extraction produced the desired monodisperse materials (based solely on SEM results). Modeling using Density Functional Theory was also incorporated into this project. The modeling was able to predict accurately the domain size and spacing vs. molecular weight for a model system, as well as accurate interfacial thicknesses.
Date: August 1, 1997
Creator: Saunders, R.S.; Small, J.H.; Lagasse, R.R.; Schroeder, J.L. & Jamison, G.M.
Partner: UNT Libraries Government Documents Department

Dynamic opto-rheological study of estane copolymers using step-scan FTIR spectroscopy

Description: Polyurethane copolymers generally consist of linear segments of polyurethane and polyester (or polyether). At room temperature, these polymers undergo a micro-phase separation, in which the polyurethane segments form hard domains while the polyester segments form relatively soft domains that act as the crosslinks between the hard cores. A wide variety of techniques has been utilized to characterize the microscopic (molecular) structure of polymeric materials. Recently, the dynamic infrared opto-rheological method has been developed, which involves the combination of dynamic mechanical analysis (DMA) and time-resolved infrared (IR) spectroscopy to study the real time IR spectral changes in polymer films under sinusoidal (or impulse) tensile stress of small amplitude. Phase-locked electronics are used to record the dynamic infrared spectral change in-phase and in-quadrature with the applied mechanical field. The result provides insight on the response to the external stress on the molecular and submolecular scale. While for relatively narrow spectral ranges this experiment is efficiently carried out by use of a dispersive spectrometer, for measurements over broader spectral windows, the use of step-scan Fourier transform infrared (S{sup 2}FT-IR) has proved to be more effective. In the study reported here, dynamic opto-rheology using S{sup 2}FT-IR spectroscopy has been applied to the polyurethane/polyester copolymer Estane 5703. Dynamic in-phase and quadrature spectra in the mid-IR region at two orthogonal polarizations have been collected, and dynamic dichroic spectra calculated and interpreted.
Date: July 1, 1998
Creator: Wang, H.; Palmer, R.A.; Graff, D.K. & Schoonover, J.R.
Partner: UNT Libraries Government Documents Department

MEAN FIELD AND MONTE CARLO MODELING OF MULTIBLOCK COPOLYMERS

Description: The authors discuss and apply extensions needed to treat multiblock copolymers within the mean field theoretical framework for microphase separation in diblock copolymer metals, originally due to Leibler. The mean field calculations are complemented by lattice Monte Carlo realizations using the bond fluctuation model. They find that the microphase separation transition occurs at larger {sub {chi}}N as the number of blocks in increased beyond two (i.e., beyond diblock), and that the characteristic length scale of the emerging morphology decreases as the number of blocks increases. The latter prediction is in qualitative agreement with published experimental results due to Sontak and co-workers for model multiblock poly(styrene-isoprene) systems and recent results due to Hjelm and co-workers for a segmented poly(ester-urethane) relevant to Los Alamos interests. Additionally, the mean field predictions and bond fluctuation realizations yield consistent results.
Date: January 1, 2001
Creator: RASMUSSEN, K. & AL, ET
Partner: UNT Libraries Government Documents Department

Molecular Self-Assembly

Description: This report is divided into two parts: a study of the glass transition in confined geometries, and formation mechanisms of block copolymer mesophases by solvent evaporation-induced self-assembly. The effect of geometrical confinement on the glass transition of polymers is a very important consideration for applications of polymers in nanotechnology applications. We hypothesize that the shift of the glass transition temperature of polymers in confined geometries can be attributed to the inhomogeneous density profile of the liquid. Accordingly, we assume that the glass temperature in the inhomogeneous state can be approximated by the Tg of a corresponding homogeneous, bulk polymer, but at a density equal to the average density of the inhomogeneous system. Simple models based on this hypothesis give results that are in remarkable agreement with experimental measurements of the glass transition of confined liquids. Evaporation-induced self-assembly (EISA) of block copolymers is a versatile process for producing novel, nanostructured materials and is the focus of much of the experimental work at Sandia in the Brinker group. In the EISA process, as the solvent preferentially evaporates from a cast film, two possible scenarios can occur: microphase separation or micellization of the block copolymers in solution. In the present investigation, we established the conditions that dictate which scenario takes place. Our approach makes use of scaling arguments to determine whether the overlap concentration c* occurs before or after the critical micelle concentration (CMC). These theoretical arguments are used to interpret recent experimental results of Yu and collaborators on EISA experiments on Silica/PS-PEO systems.
Date: November 1, 2001
Creator: CURRO, JOHN G.; MCCOY, JOHN DWANE; FRISCHKNECHT, AMALIE L. & YU, KUI
Partner: UNT Libraries Government Documents Department

Responsive Copolymers for Enhanced Petroleum Recovery

Description: The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.
Date: February 27, 2001
Creator: McCormick, C. & Hester, R.
Partner: UNT Libraries Government Documents Department

Formation of PS-b-PEO/Silica Films with Flat or Curved Multi-Bilayer Mesostructures of Large-Characteristic Length Scales Prepared by Solvent Evaporation-Induced Self-Assembly

Description: Diblock/silica films with multi-bilayer vesicular mesostructures of large characteristic length scales were synthesized through evaporation-induced self-assembly of PS-b-PEO. The present system is believed to be the first to yield diblock/silica films with multi-bilayer vesicular mesostructures through solvent evaporation-induced self-assembly (EISA). The ready formation in the present system is argued to be the polydispersity of polymer chains.
Date: November 22, 2000
Creator: YU,KUI; BRINKER,C. JEFFREY; HURD,ALAN J. & EISENBERG,ADI
Partner: UNT Libraries Government Documents Department