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Session L36 - General Poster Session II.
POSTER session, Wednesday morning, March 22
Exhibit Hall, MCC

[L36.001] Effect of starting material on ferroelectric properties of Pb_0.90La_0.15TiO_3 thin films.

Bhaskar Srinivasan (Dept. of Physics, University of Puerto Rico)

The substrate and precursor effects in sol-gel derived Pb_0.90La_0.15TiO_3 thin films were studied at various annealing temperatures in the range of 350 - 650^oC. Films for this study were prepared using acetic acid and methoxyethanol routes on Pt/Si and Pt substrates. X-ray results indicate that films prepared by acetic acid route show texturing along (100) orientation of the films with increasing annealing temperature. These film also exhibit better ferroelctric properties on Pt compared to Pt/Si substrates. Raman spectra show the stress induced softening of the lowest frequency mode with increasing annealing temperature in the films prepared by acetic acid and methoxyethanol route. However, relatively less phonon damping was observed in the methoxyethanol route processed films. The phase transition behavior in these films will be studied by high temperature Raman measurements. The structural, micro-Raman and electrical data from these films will be presented in detail. This work is supported in part by DE-FG02-91ER75764, DEPSCOR DAAG55-98-1-0012 AND NSF-DMR9801759 grants.

[L36.002] Computer Modeling of the Metal-Insulator Transition in Disordered Systems

Dain Horning, Kendall Mallory (University of Northern Colorado)

We have developed a computer model to study the effects of electron interactions on the metal-insulator transition in disordered systems. We will present some early results from this model. We have looked for the possibility of delocalized electron states existing in systems that normally exhibit only localized states.

[L36.003] Plasma Physics Calculations on a Parallel Macintosh Cluster

Viktor Decyk, Dean Dauger, Pieter Kokelaar (University of California, Los Angeles)

We have constructed a parallel cluster consisting of 16 Apple Macintosh G3 computers running the MacOS, and achieved very good performance on numerically intensive, parallel plasma particle-in-cell simulations. A subset of the MPI message-passing library was implemented in Fortran77 and C. This library enabled us to port code, without modification, from other parallel processors to the Macintosh cluster. For large problems where message packets are large and relatively few in number, performance of 50-150 MFlops/node is possible, depending on the problem. This is fast enough that 3D calculations can be routinely done. Unlike Unix-based clusters, no special expertise in operating systems is required to build and run the cluster. Full details are available on our web site: http://exodus.physics.ucla.edu/appleseed/.

[L36.004] Spin Expectation Values in Fermion Gases

Lauren Ault (The College of Wooster, Wooster OH 44691), Don Colladay (Colby College, Waterville, ME 04901)

Recently, the possibility of spontaneously breaking Lorentz invariance has been suggested in fundamental theories underlying the standard model. Resulting terms can have implications for a variety of low-energy experiments testing Lorentz and CPT symmetry. Here we investigate the effect of some of these terms on fermion gases. In some circumstances, such as thermal equilibrium, a small net expectation value on the spin of the fermion gas occurs. In addition, the number densities of left- and right-handed particles are found to differ. Some possible implications for early universe physics are discussed. This research was conducted at The College of Wooster with support from NSF-REU grant DMR 9619406.

[L36.005] First-principles study of higher-energy phases in Cu and its relation to the atomic configurations of extended defects

L.G. Wang, M. Sob (Inst. of Physics of Materials, Acad. Sci. of the Czech Republic, Brno, Czech Republic)

We performed full-potential first-principles total energy calculations for three displacive phase transformation modes in Cu. The structural and elastic properties of the ground state (fcc) and higher-energy phases (bcc and 9R), as well as the energy barrier for sliding of \111\_fcc close-packed atomic planes and the stacking fault energy were obtained. Stability of higher-energy phases in the region of extended defects is discussed in detail. Examples presented are bcc and 9R Cu in grain boundaries and bcc Cu in pseudomorphic films at low temperatures. It is shown that the higher-energy phases, which are usually unstable, can be stabilized in the region of extended defects by certain imposed constraints.

[L36.006] Dipolar interactions in systems with uniaxial symmetry

Demetris Nicolaides (Bloomfield College)

It is well known how the critical behavior of a ferromagnet, is altered considerably when one considers the effect of the long-range interaction due to pairs of magnetic dipoles in addition to the short-range spin-spin interactions. For example, the work of Larkin and Khmel'nitskii, using Feynman-graph expansions for d=3, showed that the critical behavior of a uniaxial ferromagnet with both exchange and dipolar interactions has logarithmic corrections not expected classically. This was verified with exact renormalization group equations and the \varepsilon -expansion, as well as predicted that the critical behavior of a d-dimensional uniaxial Ising ferromagnet with dipole-dipole interactions belongs in the same universality class as a (d+1)-dimensional, strictly short-range Ising ferromagnet. In the present work, an alternative approach will be used to confirm and generalize this result. It will be shown that d-dimensional uniaxial systems with isotropic short-range as well as dipole-dipole interactions have d=3 as the upper marginal dimension above which mean-field behavior fully sets in, and below which critical behavior prevails. Unlike the \varepsilon -expansion where the validity of the results depends on the smallness of \varepsilon , the method used here derives the result for any d without any constraints. The study of such systems will be done by considering a model with reduced interactions of fluctuations, allowing for the exact calculation of the partition function.

[L36.007] Ground-state Properties of One-dimensional Symmetric Periodic Anderson Model Away From Half-filling

Yan Luo, Nicholas Kioussis (Department of Physics, California State University Northridge, Northridge CA 91330-8268)

The ground-state energy, the local moment, the effective hybridization, and the projected f- and conduction density of states of the one-dimensional periodic, symmetric Anderson Lattice Model have been investigated as a function of U, V and band filling using the local mean-field (LMF) method. We have evaluated the magnetic phase diagram for the symmetric case, which shows three distinct phases: the antiferromagnetic, ferromagnetic, and Kondo phases. The antiferromagnetic phase is found to be the ground state at the half-filling and the quarter-filling cases with strong Coulomb coupling.

[L36.008] X-ray Temperature Difference Absorption Spectra (XTDAS) Analysis of Phase Transitions in NiS2-xSex (x=0.62)

Quang Le, Professor Juana Acrivos Collaboration, Boichau Nguyen Collaboration, Rizwana Shaikh Collaboration, Charles Burch Collaboration

Transmission x-ray absorption spectra (XAS) for amorphous powder NiS2-xSex (x=0.62) versus temperature (T) has been measured at the Ni and Se K-edges in the 4K to 150K temperature range to determine the presence of a temperature and composition dependent metal to insulator transition. The changes in the XAS over the temperature range support the Mott-Hubbard model, which exists at Se compositions varying between x~0.4 and x~0.6 and in the 0K to 115K temperature range.

[L36.009] Spin-Echo Decay Rates of ^29Si in URu_2Si_2 at High Temperatures

C. Rodrigues, O. O. Bernal (California State University, Los Angeles), H. G. Lukefahr (Whittier College, Whittier)

We present a study of ^29Si spin-echo relaxation in URu_2Si_2. Our measurements reveal a difference between the Hahn-echo method [\pi/2--\tau--\pi--detection] and the Carr-Purcell-Meiboom-Gill method [(\pi/2)_90^\circ--\tau--\pi--\tau--\pi\ldots detection] even at high temperatures (T\ge40~K). These results are compared with Hahn-echo and Carr-Purcell-Meiboom-Gill measurements of spin-echo relaxation in insulator and simple-metal samples. Possible origins of the high-T difference between the two methods in URu_2Si_2 are explored. We discuss our results in view of published T_2-data on URu_2Si_2.

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[L36.010] Electronic properties of single crystalline UIrGe in high magnetic fields

H. Nakotte, S. Chang (Physics Department, New Mexico State University, Las Cruces NM 88003), K. Prokes (Hahn-Meitner-Institute, NE, Glienickerstrasse 100, D-141 09 Berlin, Germany), A. H. Lacerda (National High Magnetic Field Laboratory, Pulse Field Facility, Los Alamos National Laboratory, Los Alamos NM 87545), I. Hagmusa (Van der Waals-Zeeman Institute, University of Amsterdam, Valckenierstraat, 1018 XE Amsterdam, The Netherlands)

UIrGe crystallizes in the orthorhombic TiNiSi structure and exhibits a huge magnetic anisotropy with the hard magnetization axis along the a-axis. Previous magnetic, transport and thermal studies indicated anti-ferromagnetic ordering below 15.8 K with an additional transition at 14.1 K [1]. For the present work, we have performed magnetization, magnetoresistance and specific heat measurements in magnetic fields up to 18 T. The data were taken in order to determine the magnetic phase diagrams for UIrGe in fields applied along the principle axes. [1] K. Prokes et al., Phys Rev B. 60 (1999) 9532

[L36.011] Ultrasonic measurements of UPt3 at high magnetic fields

Jeffrey R. Feller (Northwestern University, Physics Dept.), Chrong-Chu Tsai (Northwestern University), D. Dasgupta (University of Wisconsin-Milwaukee), D. G. Hinks (Argonne National Laboratory, Argonne, IL), J. B. Ketterson (Northwestern University), Bimal K. Sarma (University of Wisconsin-Milwaukee), Northwestern University Collaboration, University of Wisconsin-Milwaukee Collaboration, Argonne National Laboratory Collaboration

Ultrasound velocity and attenuation measurements have been performed on the heavy fermion compound UPt3 in magnetic fields up to 33 T and at temperatures down to 50 mK. With the field applied in its basal plane, UPt3 is known to undergo a metamagnetic transition near 20 T. This is evidenced by a large velocity dip (Dv/v > 5% at the lowest temperatures), accompanied by a peak in attenuation. The temperature- and frequency-dependence of these features will be discussed. Additional structure appears below \sim300 mK, including quantum acoustic oscillations. The field dependence of the period and amplitude of these oscillations suggest a reconstruction of the Fermi surface at the metamagnetic transition.

[L36.012] Microwave response of the heavy fermion superconductors UBe13 and U0.9725Th0.0275Be13

J. R. Feller, C. T. Lin, Chrong-Chu Tsai (Northwestern University), J. L. Smith (Los Alamos National Laboratory), J. B. Ketterson (Northwestern University), Bimal K. Sarma (University of Wisconsin-Milwaukee), Northwestern University Collaboration, University of Wisconsin-Milwaukee Collaboration, Los Alamos National Laboratory Collaboration

The superconducting transition temperature Tc of the heavy fermion system U1-xThxBe13 depends strongly on the Thorium concentration [Heffner, et al., Phys. Rev. Lett., 65, 2816 (1990)]. Tc is found to decrease monotonically from \sim0.86 K for x = 0 to \sim0.48 K for x = 0.019. For 0.019 < x < 0.043, however, two transitions are observed. These are visible as anomalies in, for example, magnetization, specific heat, and muon spin resonance data. It has been suggested that this double transition is evidence of a coexisting antiferromagnetic phase, or of a multi-component superconducting order parameter. We have measured the normalized surface impedance of two U1-xThxBe13 samples: the first with a Thorium concentration of 2.75 %, the second with no doping (UBe13). For these measurements a cylindrical copper cavity, resonated at frequencies \sim9-30 GHz, was employed. The cavity and sample were cooled using a dilution refrigerator with a top-loading feature. The temperature was varied from \sim85 mK to \sim0.9 K. Magnetic fields were also applied. The predicted double transition, with Tc1 \sim 0.6 K and Tc2 \sim 0.4 K, are observed in the doped sample. The second transition is evidenced as a kink in the resistance and a broad peak in the reactance.

[L36.013] Effects of p-p energy transfer on the pairing correlations in the one-dimensional d-p model

Zhongbing Huang, Haiqing Lin (Department of Physics, The Chinese University of Hong Kong, Hong Kong), James Gubernatis (Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545)

Using the constrained-path Monte Carlo (CPMC) method, we have studied the one-dimensional d-p model for the cases with finite Coulomb repulsion on d sites, and mainly examined the effects of transfer energy t_pp between the nearest-neighbor p sites on pairing correlations with different symmetry. Of these pairing correlations, we observed that only the tail of singlet pairing between the nearest-neighbor p sites increases explicitly with the increase of t_pp, while others decrease or increase negligibly. But for all symmetries, the vertex contributions fluctuate around zero at large distance, therefore it is difficult to determine which pairing channel dominates when the critical exponent of the correlation functions K_\rho > 1.

[L36.014] Peierls instability in a polymer chain

C.Q. Wu, Y.Z. Zhang (Phys. Dept., Fudan Univ., Shanghai, China), H.Q. Lin (Phys. Dept., Chinese Univ. of Hong Kong, Hong Kong, China)

By using a Su-Schrieffer-Heeger-type Hamiltonian, we investigate the Peierls instability in the substituted polyacetylene with lateral radical R. It is found that the Peierls dimerization along the polyacetylene chain is suppressed by increasing \pi-electron hopping between the radicals and the associated carbons. The expected quadrimerization, which is required by the Peierls theorem, does not appear in this kind of one-dimensional systems. The physical reason behind the fact is that the electronic energy gap is not again proportional to the lattice distortion as usual and then the logarithm term, which is the driving force for the Peierls instability, does not exist in the electronic energy gain of the system.

[L36.015] Elastic moduli and Entropy Considerations at the delta-epsilon Phase Transition in Pu

Timothy Darling, Albert Migliori, Joseph Baiardo, Franz Freibert, Stuart Trugman (Los Alamos National Laboratory)

Recent elastic modulus measurements by us on Ga stabilized \delta-Pu, as well as a critical examination of latent heat, elastic modulus and crystal structure data on this unusual metal suggest that some of the many structural phase transitions of Pu may be understood within a simple thermodynamic model. We show that the free energy of Pu in the FCC \delta phase and the BCC \epsilon phase, as well as the negative volume expansion coefficient of \delta can be understood and almost entirely accounted for by the phonon contributions to the entropy and the structure. We suggest that the behavior and stability of Pu is driven by the low elastic shear moduli that this material possesses, and that electronic structure calculations need only account for the low temperature monoclinic phase. Variation of the number of itinerant f electrons is unnecessary for an accurate description of the higher temperature phases.

[L36.016] Ground-State of the Single Impurity Anderson Model (SIAM) with Correlated Conduction Electrons

William J. Massano (SUNY Maritime), Jay D. Mancini, Vassilios Fessatidis (Fordham University), Samuel P. Bowen (Chicago State University)

In this work we shall consider the Hamiltonian system given by H=H_A+H_C where H_A is the usual SIAM Hamiltonian given in second-quantized notation by \[ H_A=\sum_k,sn_k,s\varepsilon _k,s +\sum_sE_sN_s+UN_rN_l+\sum_k,sV(k) \left[ c_k,sf_s+f_sc_k,s\right]. \] The interaction H_c=U_c\sum_k

[L36.017] Moments Expansion Study of the Rabi Hamiltonian

Jay D. Mancini, Vassilios Fessatidis (Fordham University), Samuel P. Bowen (Chicago State University), Robert K. Murawski (Stevens Institute of Technology)

The interaction of a single bosonic mode with a two-level fermion system has been the subject of a large number of articles in the physics literature for quite some time. For the condensed-matter physicist the boson in question is typically a phonon whereas the fermion system is represented by a two-level electron structure. The Hamiltonian which yields the appropriate physics is given by the Rabi Hamiltonian. In second-quantized notation this may be written as \[ \hatH=\frac12 ømega_0 \sigma_z+ømega b^b+ g\left(\sigma^+ b^\dagger+\sigma^+ b+ \sigma^- b^\dagger+\sigma^- b \right). \] Here the \sigma's are the usual Pauli matrices, while b and b^\dagger are the Bose operators for the (quantized) field modes. In general the natural transition frequency ømega_0 of the atom need not coincide with the boson-mode frequency ømega. In this work we shall use both the Connected Moments Expansion (CMX) and the Alternate Moments Expansion (AMX) as well as the non-perturbative Lanczos tridiagonal scheme to study the ground-state spectrum of this system. Comparisons will be made with other approximation schemes as well as ``exact" methods.

[L36.018] Generalized 2nd and 3rd order moments expansion

Robert K. Murawski (Stevens Institute of Technology), Jay D. Mancini, Vassilios Fessatidis (Fordham University), Samuel P. Bowen (Chicago State University)

A number of years ago, Cioslowski (Phys. Rev. Lett. 58, 83 (1987)) utilizing a t-expansion derived a novel expression to estimate the expectation value of the ground-state of quantum many-body systems. His derivation of a Connected Moments Expansion (CMX) was obtained through the use of a helper function. Following this work, Mancini et al.\ (Int. J. Quantum Chem. 50, 101 (1994) ) chose a different helper function to derive an Alternate Moments Expansion (AMX). The algebra of the problem suggests that there exists a set of helper functions and hence a set of unique moments expansions. In this work we present a Generalized Moments Expansion (GMX) which has as a subset both the CMX and AMX, and apply it to the harmonic oscillator.

[L36.019] Schrödinger Green's Function for an Electron in an Anisotropic Harmonic Potential in the Presence of Electric and Magnetic Fields

Vassilios Fessatidis (Fordham University)

We have examined the nonrelativistic retarded Green's function for electron motion confined by an anisotropic harmonic oscillator potential and in the presence of constant magnetic and electric fields. Here the electric field is at an arbitrary orientation with respect to the magnetic field. A closed form expression for the propagator is obtained by employing Schwinger's equation of motion operator technique.

[L36.020] Liquid Crystalline Behavior of DNA Fragments

Sean English, Shila Garg (The College of Wooster, Wooster OH 44691)

An investigation of the liquid crystalline phases of DNA fragments in different buffer solutions is reported. Previous studies have shown that a strong correlation exists between the critical concentration and the average length of DNA fragments for the observed mesophases of DNA [1]. The focus of our study is to understand the phase ordering of DNA due to changes in concentration under various boundary conditions. Previous studies have utilized evaporation as a means for increasing the concentration of the DNA samples [2]. The effects of evaporation on the development of precholesteric and cholesteric phases will be examined.

[1] K. Merchant and R. Rill, Biophys. J. 73, 3154 (1997). [2] F. Livolant, J. Physique 48, 1051 (1987). This research was partially supported by the Copeland Fund, administered by The College of Wooster.

[L36.021] Fluctuations in a near-critical steady state with temperature gradient

Alexander Patashinski (Northwestern University, Evanston Illinois), Alexander Burin (Northwestern University, Evanston, Illinois)

In liquids, temperature gradients change the large scale fluctuations due to mode coupling. For scales larger than the mode coupling radius, nonequilibrium fluctuations are stronger than equilibrium ones. Near the critical temperature Tc the mode coupling radius decreases with decreasing T-Tc, while the equilibrium correlation radius increases, and at some temperature Tcc, both characteristic lengths coincide. At Tcc>T>Tc, the fluctuations at large scales in the critical range change, the temperature gradient becomes a new relevant critical parameter; the correlation radius and the mode coupling radius as functions of this parameter yield new scaling laws. Suported by NASA Grant NAG3-1932

[L36.022] Molecular Segregation-Desegregation and Ordering: A Hybrid Computer Simulation Approach

Grace Foo (National University of Singapore), Ras Pandey (University of Southern Mississippi)

Effect of heterogeneous matrix density on segregation and orientation of short chain molecules (dimer, trimer, etc.), a model for polymer dispersed liquid crystal (PDLC), is studied by a computer simulation. The hybrid computational method involves discrete lattice and off-lattice simulations to incorporate its strength in moving the system efficiently and capturing the details; this method is also used for long chain polymer systems. On increasing the matrix density (p_b), the size of molecular aggregates is found to increase leading to a polymerization-induced segregation and seems consistent with the recent experimental observations. Orientational ordering is found to depend on the molecular weight in which the ordering decreases monotonically with the matrix density for low molecular weight liquid. For higher molecular weight liquid, on the other hand, it depends non-monotonically on the molecular weight. Similar study is also carried out at different temperatures which play an important role in clustering of molecules and their orientational ordering. Some of these results will be presented.

[L36.023] Modeling Orientational Ordering in Main-Chain LC Polymers

Paul Wessels, Bela Mulder

We present a density functional theory approach to the study of main-chain LC polymers. These polymers are modeled to consist of M slender rod-like segments joined together end-to-end. A generic bending potential between successive segments provides for a molecular flexibility mechanism. The interaction between different polymers is described by segment-segment excluded volume interactions.

The model allows the analytical determination of the isotropic-nematic (IN) bifurcation (spinodal) densities. Numerical solutions to the self-consistency equations are also obtained under various conditions. We determine the dependence of the order parameter jump \langle P_2 \rangle at the transition and the coexistence (binodal) densities as a function of the chain flexibility for several values of the chain length.

One of the advantages with working with a segmented chain model is that the generalization to other (more general) classes of systems is immediate. We illustrate this point by the application of our model to biaxial polymers and block copolymers for which we calculate the IN bifurcation densities.

[L36.024] Dielectric and Photon Correlation Spectroscopy of Filled Nematic Liquid Crystal

Fouad Aliev, Ghanshyam Sinha (Department of Physics, University of Puerto Rico, PR 00931)

Nematic liquid crystal filled with aerosil particles has been investigated by broadband dielectric spectroscopy (BDS) and photon correlation spectroscopy (PCS). The aerosil particles of diameter \simeq 10 nm in filled nematic liquid crystals form a network structure with linear size of LC domains about 250 nm and with random distribution of the director orientation of each domain. This material has a very developed liquid crystal-solid particle interface that makes the role of the surface layers of LC important in the determination of the properties of the material. BDS provides information on reorientational motion of polar molecules of liquid crystal while PCS probes dynamics of collective modes associated with director fluctuations. We found that the properties of 5CB are considerably affected by the network. Two bulk-like dielectric modes due to the rotation of molecules around short axes and the tumbling motion were observed in filled 5CB. Additionally, a low frequency relaxation process and dispersion of dielectric permittivity due to conductivity were observed. The treatment of the surface of filling particles has strongest influence on the properties of the slow process and it is less important for molecular modes. PCS experiment shows that two new relaxation processes appear in filled 5CB in addition to the director fluctuations process in bulk.

[L36.025] Molecular and Collective Relaxation in Liquid Crystals Partially Filling Cylindrical Pores

Zaira Nazario, Timofei Krouglov, Ghanshyam Sinha, Fouad Aliev (Department of Physics, University of Puerto Rico, PR 00931)

We have investigated the influence of layer thickness on dynamical behavior of liquid crystal (LC) - 8CB - partially filling cylindrical pores by dielectric and photon correlation spectroscopies (PCS). Layers of different thickness are formed on the pore walls as a result of controlled impregnation of porous matrices (Anopore membranes). Dielectric spectra of samples with different LC layer thickness consist of the main peak (f_m \sim 5 MHz) due to the reorientation of molecules around short axis and secondary peak (f_m \sim 50 MHz) - tumbling mode - with much smaller amplitude. Since the probing electric field was parallel to the pore axis the presence of the tumbling mode suggests that the orientation of molecules in partially filled pores is not perfectly axial. The relative contribution of the tumbling process increases with the decrease of the thickness of LC layer. The main relaxation process broadens and its relaxation times decrease with decreasing thickness. Results on structure and orientation in surface layers obtained in PCS experiments, probing collective dynamics of director fluctuations, were consistent with dielectric data. These experiments allow clarifying the role of the surface layers on the physical properties of geometrically restricted LC.

[L36.026] Liquid crystals in the SiO_2 opals

Daeseung Kang, Joseph E. Maclennan, Noel A. Clark (Department of Physics and Ferroelectric Liquid Crystal Materials Research Center, University of Colorado, Boulder, CO), Ray H. Baughman (AlliedSignal Corp., Morrstown, NJ)

We have investigated the electro-optical properties of liquid crystals (LCs) that are confined in a regularly arranged opal structure. It is known that periodic structures of dielectric solids can exhibit photonic band gaps. Three-dimensionally periodic structures made of SiO_2 spheres with the diameter ranging from 100 to 400 nm are realized by a sedimentation process between two ITO glass plates. The empty space is then infiltrated with a liquid crystal. An external electric field applied on the LC-opal composite changes the effective refractive index and, as a consequence, alters the stop band wavelength. Additionally we have made inverse opal structures by replacing the liquid crystal with a polymer matrix, and then by extracting the SiO_2 particles. Field induced phenomena on the LC-inverse opal are discussed. This work was supported by the NSF MRSEC Grant DMR 98-09555, the NSF Grant DMR 96-14061 and the NASA Grant NAG3-1846.

[L36.027] Structure and Phase Determination of Laterally Attached Side-Chain Liquid Crystalline Polynorbornenes with a One-Carbon Spacer

Gue-Hyun Kim, Coleen Pugh, Stephen Z. D. Cheng* (Maurice Morton Institute and Department of Polymer Science, The University of Akron, Akron, Ohio 44325-3909)

A series of polynorbornenes (PNBEs) with 1,4-bis[(3´-fluoro-4´-n-alkoxyphenyl)ethynyl] benzene mesogens (n = 9-12) laterally attached to the polymer backbone through a one-carbon spacer was synthesized by ring-opening metathesis polymerization of the corresponding norbornene-based monomers. Wide angle X-ray diffraction experiments demonstrate that the mesogens organize into the tilted layer structure of a smectic C phase at room temperature, and polarized light microscopy demonstrates that the highest temperature phase is a nematic phase. Upon heating above room temperature, the tilt angle of the smectic C phase of all of the PNBEs (n = 9 - 12) continuously decreases, especially at temperatures above 60°C. However, the smectic C phase of PNBE (n = 12) transforms to a smectic A phase at 85 °C, whereas the smectic C phase of the PNBEs (n = 9 - 11) transforms to a N phase. The phase transformation between the smectic C and the smectic A phases is characterized by a second-order transition.

[L36.028] DENDRITIC GROWTH IN NEMATIC LIQUID CRYSTALS

Joshua Martin, Shila Garg (The College of Wooster, Wooster OH 44691)

The experimental study of the onset of electrohydrodynamic convection (EHC) through a dendritic growth is reported. If a magnetic Freedericksz-distorted liquid crystal of negative dielectric anisotropy is subjected to an electric field parallel to the magnetic field, EHC sets in through the nucleation of dendrites [1,2]. Measurements of tip speeds of the dendrites as a function of applied voltage at a fixed magnetic field are made. The goal is to explore the effect of the magnetic and electric fields on the dendritic growth. In addition, pattern dynamics is monitored once the final state of spatio-temporal chaos is reached by the system. [1] J. T. Gleeson, Nature 385, 511 (1997). [2] J. T. Gleeson, Physica A 239, 211 (1997). This research was supported by NSF grants DMR 9704579 and DMR 9619406.

[L36.029] The influence of ions on the "V-shaped" electrooptic response of ferroelectric liquid crystals with high spontaneous polarization

Martin Copic, Danielle Bundy, Joseph E. Maclennan (Affiliation), Noel A. Clark (Ferroelectric Liquid Crystal Materials Research Center, Department of Physics, University of Colorado at Boulder, CO 80309-0390)

It has recently been shown that in surface stabilized ferroelectric liquid crystal (SSFLC) cells with high spontaneous polarization the polarization charge self-interaction leads to a so-called "V-shaped" optical response to an applied voltage. The presence of ionic free charges in the liquid crystal, however, changes the internal electric field and therefore also the spatial dependence of the polarization and optic axis orientation. We have numerically solved the nonlinear ion diffusion equation in the electric field due to external voltage, spontaneous polarization and ions, and calculated the electrooptic response to a triangular applied voltage. When the period of the driving voltage is smaller than the zero-field diffusion time of the ions across the cell and larger than the ion transit time in the applied field, an inverse hysteresis in the electrooptic response is obtained, in agreement with experimental observations. At these time scales ions also cause characteristic changes in the shape of the electrooptic response. This work was supported by NSF MRSEC Grant DMR 98-09555 .

[L36.030] Depletion and Reentrant Phase-transitions with Colloids and Dendrimers

A. G. Yodh, Jian Zhang, Subrata Sanyal (Department of Physics amp; Astronomy, University of Pennsylvania, PA 19104)

Starburst Polyamidoamine (PAMAM) dendrimers represent ``dense star'' polymers that unlike classical polymers have specific size and shape characteristics, a high degree of monodispersity and molecular uniformity. Using optical microscopy, we have studied systems composed of aqueous suspensions of charged polystyrene colloids and ``generation'' 9.5 PAMAM dendrimers. Depletion-mediated crystallization of colloids is observed. In addition, an entropy-driven reentrant phase behavior (liquidlike to solidlike to liquidlike) of colloids is tentatively observed with the systematic increase of dendrimer concentration and a fixed colloid concentration.

[L36.031] Structural Relaxation of Soft Giant Micelles with Liquid Like Order

Reinhard Sigel (FO.R.T.H.-IESL Heraklion, Crete, Greece), Stergios Pispas (Department of Chemistry, University of Athens, Athens, Greece), Dimitris Vlassopoulos (FO.R.T.H.-IESL Heraklion, Crete, Greece), Nikos Hadjichristidis (Department of Chemistry, University of Athens, Athens, Greece), George Fytas (FO.R.T.H.-IESL Heraklion, Crete, Greece)

In a selective solvent, diblock copolymers form micelles consisting of colloid like cores and tethered polymer "hairs". Liquid like order of these soft colloids gives rise to a maximum in the structure factor S(q), which for high polymeric molecular weight is accessible by dynamic light scattering. While a pronounced slowing down of the collective diffusion at the maximum position is well known for hard spheres, which just reflects an enhanced lifetime of the fluctuation with the largest amplitude, a similar effect is not observed for micelles with long hairs (hairy micelles). A coupling of translational and rotational motion due to shearing forces is suggested as an explanation. On going to micelles with shorter hair, the slowing down is partly recovered. In addition to the diffusion dynamics, the scattering data show two relaxation modes, which arise from the motion of the hairs and are also detected by dynamic mechanical experiments. They barely depend on q and - in contrast to the viscosity - on the concentration.

[L36.032] Heat Transfer and Onset of Convection in a Very Compressible Fluid

Andrei Kogan, Horst Meyer (Duke University)

The heat transfer has been studied in a Rayleigh-Bénard cell filled with ^3He at the critical density over the reduced temperature range 5\times10^-4 < \epsilon < 0.2 where \epsilon = (T-T_c)/T_c with T_c = 3.316 K. The experiment consisted in measuring the temperature difference \Delta T(t) across the fluid layer as a function of time after turning on a constant vertical heat current q. The height of the fluid layer was 1 mm and the aspect ratio \Gamma = 57. The thermal conductivity in the non-convective state and the onset of convection were determined, and measurements were made of \Delta T(t = \infty) as a function of q up to reduced Rayleigh numbers (Ra-Ra_c)/Ra_c of the order of 5 \times 10^3. The onset of convection agreed well with predictions combining the Schwarzschild and Rayleigh criteria. As q is increased beyond the onset of convection, several qualitatively different patterns in \Delta T(t) are observed until the steady state is reached. These patterns, among them unusual oscillatory ones, change as q and \epsilon are varied and a map of the various features in \Delta T(t) is presented in the [\Delta T(\infty), \epsilon] plane. The power spectrum in the convective regime will also be discussed. The transient measurements of \Delta T(t) in the non-convective regime were in very good agreement with predictions based on the theory by Onuki and Ferrell.

[L36.033] Twisted and Braided Vortices in Rotating Channel Flow

Jessica Levine, Joseph Niemela (University of Oregon)

We report observations of two types of secondary flow patterns in a channel flow subject to spanwise rotation: twisted and braided vortices. These states have many similarities to those patterns first observed in Taylor-Couette flow (TVF) by Andereck, Dickman and Swinney (Phys. Fluids 26, 1983) and can coexist at the same Reynolds number. The streamwise wavenumber, corresponding to the twists, or to the spacing of vortex crossings, has broadband components in the power spectrum, as in the case of TVF. The spectrum is determined from light intensity measurements at a particular downstream point as the vortices are swept by. A 1.75% by volume mixture of Kalliroscope flakes in water is used for flow visualization and reflectance measurements. A laser beam is transmitted across the channel width and scattered light is detected off-axis by a sensitive fast photodiode with wide angle collection optics. With span-to-width aspect ratios as small as 2, single braided roll pairs are observed. Spatial and temporal characteristics are observed as a function of Reynolds and Rossby number. Research supported by NSF grant CTS-9422442.

[L36.034] Flow Through Layered Porous Media in Gradient Field: Response of Flux Rate and Density Distribution

Ras Pandey (University of Southern Mississippi), Joe Gettrust (Naval Research Laboratory)

A lattice gas model is used to study the flow of gas (methane) within marine sediments with simplified pressure and temperature gradient conditions. The porous sedimentary material is described by a matrix on a discrete lattice. Geologic fault zones, in which the porosity is higher than the surrounding material are imbedded in the model. The bottom layer of the matrix is connected to a source of gas, which is modelled by particles with simplified particle-particle, particle-pore, and particle-barrier interactions. The Metropolis algorithm is used to move the gas particles, which are driven by the density gradient at the source, temperature, and a pressure gradient, from bottom to the top of the model where gas particles can escape the system. In this non-conservative open system, a steady state is accomplished for both the flow rate and the density distribution. Response of the flow rate is studied in detail as a function of pressure and temperature gradient. Both linear and nonlinear responses of the flow rate are observed and the crossover regime is identified. We show that the steady-state density profile depends on porosity, magnitude of the field, and the temperature. Some specific profiles and flow predictions will be presented.

[L36.035] Self-consistent Approach to Finite-Temperature Excitations in Dilute Bose Gases

Emil Lundh, P. Ao, Lars M. Jensen (Dept.\ of Theoretical Physics, UmeåUniversity, S-90187 Umeå

Using a path-integral approach, we develop a self-consistent theory of excitations at finite temperature for dilute Bose gases. The use of pairing fields \langle \psi \psi \rangle, \langle\psi^\psi \rangle ensures validity in a broader temperature range than the traditional condensate-wavefunction approach can offer. We derive Bogoliubov equations, dispersion relations and critical temperatures for both homogeneous and trapped systems.

[L36.036] Strongly interacting one-dimensional Bose condenstates

B. Tanatar (Bilkent University)

We study the interaction effects on the condensates by considering a model of one-dimensional bosons. The power-law type external potential allows for the formation of a condensate in these systems. Using a density-functional theory type formalism we obtain an equation describing the condensate wave function in the limit of very strong interactions between the bosons. The properties of the condensate in the model system with strong interactions are investigated.

[L36.037] Harmonically Trapped Quantum Gases

M. Grether (Facultad de Ciencias, UNAM, México D.F., México), M. Fortes (Instituto de F\'\isica, UNAM, México D.F., México), M. de Llano (Instituto de Investigaciones en Materiales, UNAM, México D.F., México), J.L. del R\'\io (UAM, Unidad Iztapalapa, México D.F., México), F.J. Sevilla, M.A. Sol\'\is, S. Tapia (Instituto de F\'\isica, UNAM, México D.F., México), A.A. Valladares (Instituto de Investigaciones en Materiales, UNAM, México D.F., México), Universidad Autónoma Metropolitana Collaboration, Universidad Nacional Autónoma de México Collaboration

We solve the problem of an ideal boson or fermion gas in d-dimensions trapped by \delta \leq d mutually perpendicular harmonic oscillator potentials and obtain the general density of states from which thermodynamic properties such as internal energy, specific heat, etc. can be determined. The trapped system is identical that of the corresponding ideal quantum gas in d+\delta dimensions but with an effective mass that vanishes in the thermodynamic limit.

[L36.038] Stability of Vortices in Two-component Bose Condensates

Hualin Shi, Sui-Tat Chui (Bartol Research Institute, University of Delaware)

We study the stability of vortices in two-component Bose condensates by means of Monte Carlo simulations. The total energies of condensates with different vorticity have been calculated. The global stability has been analyzed with and without rotating fields. We study the local stability of vortices prepared in the recent JILA experiment (M. R. Andrews et al., Phys. Rev. Lett. 83, 2498 (1999)), where there are two available configurations in which one specie has vorticity m=1 and the other one has m=0. The relationship between the stability with the interacting strengths has been studied. We find both of configurations are not locally stable when the interacting strengths are weak, but when the interacting strengths are strong enough both of configurations are locally stable. At a certain condition, one configuration is locally stable and the other one is not.

[L36.039] Excited States of a Bose Condensate in a Harmonic Trap

Kunal Das, T. Bergeman (SUNY Stony Brook)

Experimental observations [1,2]of some of the modes of lowest frequency above a Bose condensate in a harmonic trap raises the question whether higher modes might also be observed. A systematic study of various modes would provide valuable diagnostics for the Bose condensate regime and might also provide useful research tools, analogous to atom Rydberg states. Using the Hartree-Fock Bogoliubov equations and discrete variable representation methods [3], as well as perturbation approaches, we have calculated energies as a function of atom number, atom-atom interaction and temperature. For a spherically symmetric trap, we find that asymptotically, the energies approach the bare harmonic oscillator values as 1/sqrt(n), where n is the number of radial nodes. We have begun to address the crucial question of widths, taking into account Landau and Beliaev processes. Our first results, also for spherical symmetry, indicate that as a function of energy, the widths vary somewhat randomly about a slowly decreasing trend. We will discuss means to excite these resonances selectively by off-resonance modulated laser light or by stimulated Raman scattering. 1. D. S. Jin et al. Phys. Rev. Lett. 78, 764 (1997). 2. D. Stamper-Kurn et al., Phys. Rev. Lett. 81, 500 (1998). 3. T. Bergeman et al., abstract this meeting.

[L36.040] Studies of surface spin waves and exchange interactions

Mark van Schilfgaarde (Sandia Nat.Lab.,Livermore,CA), Vladimir Antropov (Ames Lab,Ames,IA)

A layer version of the tight-binding LMTO-GF method was used to obtain exchange interaction parameters and spin wave spectrum at the surface of elementary ferromagnets (Fe,Ni,Co) with the local spin-density functional approximation. Different ways of calculating of exchange parameters in density functional approach were used and the results compared. The stability and characteristic range of surface spin wavecompare to bulk ones have been estimated and possible connection with experimental data emphasized.

[L36.041] GW quasiparticle bandstructure of YH_3

Takashi Miyake, Ferdi Aryasetiawan (JRCAT-ATP, 1-1-4 Higashi, Tsukuba, Ibaraki 305-0046, Japan), Hiori Kino (Institute for Solid State Physics, University of Tokyo, Roppongi, Minato-ku, Tokyo 106-8666, Japan), Kiyoyuki Terakura (JRCAT-NAIR, 1-1-4 Higashi, Tsukuba, Ibaraki 305-8562, Japan)

We present the bandstructure of YH_3, which exhibits a metal insulator transition under continuous increase of hydrogen concentration from 2 to 3. Although LDA calculations suggest that the trivalent hydride has no band gap unless we assume a complicated structure, the quasiparticle band with the GW approximation reproduces insulating behavior. The role of the self-energy correction is to raise the unoccupied Y4d band rather than to decrease the band-width of the occupied H1s band. The results will be compared with other theories which are based on model Hamiltonians. The effect of the self-consistency will be also discussed.

[L36.042] A Database of Fermi Surfaces in Virtual Reality Modeling Language

Tat-Sang Choy, Jeffery Naset, Selman Hershfield, Christopher Stanton (Physics Department, University of Florida), Jian Chen (Seagate Technology)

We have built a database of Fermi surfaces in Virtual Reality Modeling Language (VRML) for 45 elemental solids. Running any of the free VRML browsers on an entry level personal computer, a user can rotate and fly through the 3-dimensional Fermi surfaces in real time. The homepage of the database contains a periodic table that links to the Fermi surface pages of individual elements. For each of the solids, the Fermi surface of a band that crosses the Fermi level is contained in one of the 167 VRML files. The average size of the files is less than 70KB. To obtain the Fermi surfaces, the energy E(k) in k-space is calculated using a nine-band tight-binding model. The energy data is then passed through an isosurface generator which also clips the surfaces with the boundary of the first Brillouin zone. The website also provides a CGI script which returns Fermi surfaces in VRML using user-submitted energy data. The homepage of the database is \underlinehttp://www.phys.ufl.edu/fermisurface .

[L36.043] Tight Binding Electronic Structure Calculation of (GaAs)_n/(Ge_2)_n (2 \leq n \leq 4)

Jeffrey Rufinus (University of Wisconsin)

We have performed a calculation of electronic structure of (GaAs)_n/(Ge_2)_n Superlattice (2 \leq n \leq 4) with Tight Binding Method. We have found that the band-gaps are direct. Previous self-consistent pseudopotential calculations also showed that in the range of ( 2 \leq n \leq 4) the band-gaps of (GaAs)_n/(Ge_2)_n are direct.

[L36.044] Electronic excitations in II-VI compounds from an ab-initio GW approach

Andrzej Fleszar, Werner Hanke (Inst. for Theoretical Physics, University of Würzburg, 97074 Würzburg, Germany)

The electronic excitation spectrum in baryllium, magnesium, cadmium and mercury chalcogenides has been calculated by means of the ab-initio GW approximation using norm-conserving pseudopotentials, plane-waves or mixed-basis expansions, and including the spin-orbit interaction. Both real and imaginary parts of self-energy have been obtained, thus giving insight into the dynamics of quasiparticles: besides the correlated band structure, we present the excitation-energy dependence of the lifetime and the inelastic-mean-free path of hot electrons and holes. The GW energy bands compare very well with ARPES data for all materials studied except the mercury compounds, where there are still significant differences. In addition to the one-particle energy spectrum we present EELS. ellipsometry and soft-x-ray resonant inelastic scattering spectra.

[L36.045] The efficiency of the generalized simulated annealing

Y. Xiang, X. G. Gong (Institute of Solid State Physics, Chinese Academy of Sciences, Hefei-230031, China)

We have explored the efficiency of the generalized simulated annealing (GSA) [1] through a comparable study with the classical simulated annealing (CSA) [2] and the fast simulated annealing (FSA) [3]. Our calculations on the Thomson model and nickel clusters show that the relative efficiency of GSA to CSA and FSA increases exponentially with the number of variables of the objective function. We have also observed a larger exponential factor in optimizing the structures of Ni clusters than that in the Thomson model. Thus, relative to CSA and FSA, the more complex the system is, the more efficient the GSA method is. The possible reason for GSA with high probability in finding the global minimum is also addressed through searching a two-dimensional phase space in a low temperature.

[1] C. Tsallis and D. A. Stariolo, Physica A 233, 395(1996).

[2] S. Kirkpatrick, C. D. Gelatt, Jr., and M. P. Vecchi, Science 220, 671(1983).

[3] H. Szu. and R. Hartley, Phys. Lett. A 122, 157(1987).

[L36.046] Further Consequences of the Canonical sequence Method in Quantum Many-Body Systems

Vassilios Fessatidis, Jay D. Mancini (Fordham University), Robert K. Murawski (Stevens Institute of Technology), Samuel P. Bowen (Chicago State University)

A number of years ago, Horn and Weinstein (Phys. Rev. D30, 1256(1984)) introduced a novel nonperturbative method for calculating ground-state expectation values for Hamiltonian systems. Although close in spirit to standard variational schemes this ``t-expansion" introduces a fictional parameter t to the trial state \exp(-\hatHt/2) |\Phi\rangle wherein the limit t\rightarrow \infty yields convergence to the ground-state energy E_0 for the expansion \[ \lim _t\rightarrow \infty \frac\left\langle \Phi \right| \hatH \exp \left( -\hatHt\right) \left| \Phi \right\rangle \left\langle \Phi \right| \exp \left( -\hatHt\right) \left| \Phi \right\rangle =E_0. \] Recently Samaj et al.\ (J. Phys. A30, 1471(1997)) have generalized the t-expansion technique and the related Connected Moments Expansion to a more general canonical sequence. They then apply this canonical series to the quantum Ising model. In the present work we have expounded upon the work of Samaj et al.\ and have applied this to a number of different many-particle Hamiltonian systems.

[L36.047] Variational Approach for Approximating the Ground-state Energy of the Rabi Hamiltonian

Samuel P. Bowen (Chicago State University), Vassilios Fessatidis, Jay D. Mancini (Fordham University), Robert K. Murawski (Stevens Institute of Technology)

In this work a recently developed variational technique (Phys. Rev. A51, 3337 (1995)) is applied in the estimation of the ground-state energy of the Rabi Hamiltonian \hatH=\frac12 ømega_0 \sigma_z+ømega b^b+ g\left(\sigma^+ b^\dagger+\sigma^+ b+ \sigma^- b^\dagger+\sigma^- b \right). For a trial wavefunction we use a single parameter coherent state of the form \left| \Psi _0\right\rangle =N_0\,e^\alpha b^\dagger \left| 0\right\rangle \left( \left| \downarrow \right\rangle - \left| \uparrow \right\rangle \right) and a finite non-orthogonal basis is generated. This is a generalization of the Linear Variational Method used by quantum chemists. Our results are compared to those of Bishop et al.\ (Phys. Lett. A254, 215 (1999)), where a large scale diagonalization of the hamiltonian was performed.

[L36.048] A Parallel AMR version of the PPM Hydrodynamics Code

Dennis Dinge (The Laboratory for Computational Science and Engineering at The University of Minnesota and Hamline University), Paul Woodward (The Laboratory for Computational Science and Engineering at The University of Minnesota)

The Piecewise Parabolic Method (PPM) hydrodynamics code and other codes based on the PPM technique have been used extensively for the simulation of astrophysical phenomena. A new version of the PPM code under development at the the University of Minnesota's Laboratory for Computational Science and Engineering (LCSE) will be described. This new code incorporates a version of dynamic local adaptive mesh refinement (AMR) targeted specifically at improving the treatment of flow around shocks and contact discontinuities. Because the AMR is targeted at surfaces within a flow that can develop complex shapes, a cell-by-cell approach to the grid refinement is adopted in order to minimize the number of fine grid cells, with the hope of controlling the computational cost. Information is saved from the coarse grid solution in order to reduce the difference stencil for refined grids, also with the goal of reducing cost. The data structures and parallization method are being carefully designed to permit efficient implementation of the algorithm on clusters of shared memory machines, with automatic dynamic balancing of computational loads over the cluster members. Sample results in 2-D will be presented.

[L36.049] Dimensional Crossover of the XC Density Functional

P. Garcia-González (University of York)

In the Density Functional Formalism, the ground state energy of any electron system is given by an unique universal functional of the density. As a consequence, the same functional must be able to describe systems confined in any number of spatial dimensions. Concretely, the expression of the functional for a 2D system should result from the 3D one applied to a system where the density profile is a delta function along one of the coordinates. In this work, we present a study on the ability of several models for the exchange-correlation (XC) energy to verify this property. We obtain the behavior of various well known approximations in the strict 2D limit. We show that the LDA and GGA approximations diverge. However, the weighted density approximation (WDA) gives an accurate XC energy for the 2D electron gas as well as a good description of its pair correlation function. The above theoretical study is illustrated by applying these models to more realistic quasi-2D electron systems.

[L36.050] First principles study of the Raman spectra of SiS_2 and SiSe_2

Shau Grossman, Koblar Jackson (Physics Dept., Central Michigan University, Mt. Pleasant, MI 48859)

Raman spectroscopy has long been used as a probe of the atomic structure of chalcogenide glasses. Sharp features in the spectra indicate the presence of characteristic structural units, but the Raman measurements alone cannot directly determine the atomic arrangements in these units. In this presentation we discuss calculations based on the density functional theory (DFT) that are aimed at interpreting the spectral peaks in atomistic terms. The calculations yield both the frequencies and Raman spectral intensities for the vibrational modes of cluster models of the materials. We create simulated spectra by combining results of several cluster calculations. Here we focus on SiS_2 and SiSe_2. The simulated spectra for these materials are in good agreement with experiment. We contast the results for these glasses with previous calculations for the Ge-analogues, GeS_2 and GeSe_2 and discuss the structural implications of the differences. Work supported by Research Corporation and NSF DMR-9972333

[L36.051] The Fractal Structure of Basic Particles

Shuming Li (University of Science & Techmology Hebei), Lihua Li (University of Minnesota), Shuyun Li (Shijiazhuang Vocational Technology College), Shuwei Li (Hebei BoAi Hospital)

A single photon with very high energy can form a tiny black hole bound by its gravitational force, whose state is referred as Space-Time Quantum of Action (STQA). The Schwarzschild radius, energy and duration of STQA can be calculated. It is very intriguing to find out that the product of space interval, energy and time interval of STQA is a constant (STQAC). In addition, STQAC is proven to be the minimum of all particles, which means that the product of space interval, energy and time interval for other particles is integer times as much as STQAC. Thus it is reasonable to hypothesize that the STQA is the basic unit of all kinds of particles. We deduced that STQAs construct all the particles in various fractal dimensions. The dimension of the universe is calculated to be three. Since the product of energy and time interval of the basic unit STQA is the Plank constant, the real quantum of action can be found, which leads to a new explanation to the in-determinant principle of Quantum theory. We can foresee many practical applications of this finding. One example is the novel design of fractal antennas that might lead to revolution in wireless communications.

[L36.052] Infrared Photoablation Studies of Arsenic Selenide with the Vanderbilt FEL

Janet Adair, Zsuzsanna Marka, Mike Albert, Shailesh Singh, Norman Tolk (Vanderbilt University, Nashville TN)

In recent years arsenic selenide has shown a high potential for application as an infrared fiber material. It transmits in most of the 2-10 micron region, which is available at the Vanderbilt Free Electron Laser (FEL). The ablation threshold was measured for the bulk material at several different wavelengths corresponding to impurity absorption, such as Se-H and C-H vibrational modes. Using a time of flight spectrometer to detect the ablated particles, individual As/Se ions as well as bigger clusters of ~6 As/Se atoms were observed. The Vanderbilt FEL delivers 3-5 microsecond long macropulses which consist of 1 ps long micropulses separated by 350 ps. Previous threshold measurements were made with the entire length of the macropulse hitting the sample. In the future a Pockel cell will be used to reduce the length of the macropulse to investigate the pulse length dependence of the ablation process. (Work funded by ONR)

[L36.053] Length Scale of Spatially Heterogeneous Dynamics in Supercooled Glycerol

XH Qiu, M.D. Ediger (University of Wisconsin-Madison), S.A. Reinsberg (Max-Planck-Institut fuer Polymerforschung)

Studies on a number of fragile glass formers has shown that the non-exponential \alpha-relaxation at temperatures close to T_g can be attributed to the existence of spatially heterogeneous dynamics. We have applied a recently developed multidimensional solid-state NMR method to measure the length scale of dynamic heterogeneities for the first time to a low molecular weight glass former. The length scale in glycerol was determined to be about 0.6 nm, much shorter than the length scale of 2-3 nm found in poly(vinyl acetate). This difference may be related to the fact that glycerol is a stronger glass former than poly(vinyl acetate). Since the heterogeneity length is an upper bound for the length scale associated with cooperative motion, our result is an interesting test for current theories of the glass transition.

[L36.054] Fluid Viscosity Analogs in Granular Materials

Amaria George, Osiel Bonfim (Reed College)

Viscosity is a major factor contributing to the dynamical behavior of a fluid system. Fluid viscosity is responsible for the resistive force experienced by objects moving through a fluid, and is directly proportional to the drag force on an object. Since granular materials exhibit many fluid-like properties, it is natural to assume the existence of a granular viscosity analog. We measure the granular drag force on cylindrical and spherical objects, and we compare it to the cross-sectional area and the insertion depth of the objects in granular materials to determine the mathematical dependence of the drag force on these parameters. From this relation, we determine a granular form of Stokes' Law.

[L36.055] BEAD PILE SYSTEM AS A MODEL FOR SELF-ORGANIZED CRITICALITY

Hanna L. Wagner, Donald T. Jacobs (The College of Wooster, Wooster OH 44691)

In 1987, Bak, Tang, and Wiesenfeld introduced a new paradigm in the physics of large, complex, dynamical systems called Self-Organized Criticality. One system that has previously been used as a model for SOC is a sandpile. We experimentally investigated smooth glass beads forming a conical pile, where adding one bead at a time causes many small, and a few large, avalanches. The size distribution of avalanches was consistent with the predictions of Self-Organized Criticality. In particular, the number of avalanches of a given size was proportional to the size of the avalanche to the power (-1.47±0.09), which is close to the mean-field prediction of –1.40±0.03. This result was independent of the size or shape of the base of the pile. We were also able to determine the power spectral density, which exhibited a power-law with slope -1.80±0.09 that was also independent of base size and shape. This research was supported by NSF-REU grant DMR 9619406.

[L36.056] Exploring Subsurface Detail of Axial Segregation in Binary Mixtures of Glass Beads in a Horizontal Drum Mixer by Mechanical Means

Kevin A. Parendo (University of Minnesota -- Morris), Joel M. Hanson, James A. Flaten

We have studied axial segregation of mixtures of 2.0 mm and 0.90 mm soda-lime glass beads in a 5"-diameter, 22.5"-long horizontal drum mixer. ``Reversible" axial segregation is apparent on the surface down to concentrations of about 20/much of the segregation action occurs beneath the avalanching surface and cannot be inferred from surface observations. We have used a variety of mechanical techniques to characterize the subsurface segregation. Although mechanical probing is somewhat invasive, a combination of "freezing" bead packs in gelatin, sieving bead packs axially, and cutting into dry bead packs to examine subsurface structure has allowed us to document the time evolution of reversible axial segregation in a 50%-small, 50%-large bead mixture.

[L36.057] Droplet Vorticity Alignment in Model Polymer Blends

Kalman Migler (NIST, Polymers Division)

The shear induced deformation of polymeric droplets in an immiscible polymeric matrix is studied using a transparent rotating plate-plate device. We consider the case where the viscosity ratio of the two phases is near unity, but the elasticity ratio of the droplet to the matrix is of order 10^2. This is achieved by using a matrix of PDMS and a droplet of a PIB based Boger fluid. In the limit of weak shear and small droplets, the droplet alignment is along the shear direction, whereas for strong shear and large droplets, the alignment is along the vorticity direction. There is a range of conditions for which alignment can be along either axis. For droplets aligned along the vorticity axis, the distribution of aspect ratios is broad. The transformation from flow alignment to vorticity alignment upon commencement of shear flow has been observed and correlates with the time scale for development of normal forces in the Boger fluid.

[L36.058] Multilayer Coextrusion Reveals Slip at Polymer-polymer Interfaces

Rui Zhao, Christopher W Macosko (Department of Chemical Engineering and Materials Science,University of Minnesota)

De Gennes (1992) suggested that loss of entanglement in the interfacial region between two incompatible polymers causes slip at interfaces. Goveas and Fredrickson (1998) developed a quantitative model for the lowering of interfacial viscosity. However, to date there appears to be no quantitative experimental evidence for interfacial slip. We coextruded polypropylene and polystyrene with closely matched viscosities into multilayers with 2,32 and 128 layers. Pressure drop of the coextruded multilayer melts through a slit die was measured. The data showed a 40reduction when the number of layers increased from 2 to 128, which indicates interfacial slip. The steady shear viscosity of the multilayer sample was also measured in parallel plates. When the shear stress was higher than a critical value, the viscosity of the multilayers was lower than either of the components. The interfacial viscosity was estimated, and 40 times reduction was observed. Diblock copolymer which spanned the interfaces was shown to able to suppress interfacial slip.

[L36.059] Electrospinning from a Polymer Melt in a Vacuum

Ratthapol Rangkupan, Darrell H. Reneker (Maurice Morton Institute of Polymer Science, The University of Akron, Ohio 44325-3909)

Electrospinning from polymer melts in a vacuum was studied. Fibers of polypropylene, high-density polyethylene and poly(ethylene terephthalate) were successfully electrospun. The molten polymer was held in a glass tube. A metal wire immersed in the molten polymer supplied charge, which migrated through the melt to the surface exposed at the end of the glass tube. The electrical forces overcame both surface tension and the viscous forces within the polymer melt, and ejected charged jets of molten polymer. The jets were attracted to an aluminum sheet maintained at an attractive electrical potential, where they solidified. The motion of the larger jets could be followed by eye. The diameters of the solidified jets ranged from 3 to 60 microns in these preliminary experiments. The vacuum process is being investigated because the magnitude of electric fields produced in a vacuum are not limited by the low dielectric breakdown strength of air.

[L36.060] JET-SPLITTING INSTABILITY IN ELECTROSPINNING OF POLY(2-HYDROXYETHYL METHACRYLATE)

Sureeporn Koombhongse, Darrell H. Reneker (Maurice Morton Institute of Polymer Science, The University of Akron, Akron, Ohio 44325)

The electrically charged surface of a polymer fluid becomes unstable when the electrical forces overcome forces of surface tension. A charged jet is then ejected from the surface. The electrical charge carried with the ejected jet can excite instabilities of the jet, which affect its path. A bending instability [1] is frequently observed. In some solutions of poly(2-hydroxyethyl methacrylate) (HEMA), high speed videographic images show that a splitting instability also occurs for the more concentrated solutions. In the splitting instability, a smaller, straight jet is ejected from the primary jet. The splitting instability may be observed before or while the bending instability is growing. In a 20instabilities are dominant. The bending instability became observable when the concentration was reduced to 16more dominant when the concentration was further reduced to 16 1. D. H. Reneker, A. L. Yarin, H. Fong, S. Koombhongse, J. App. Phys, to be published.

[L36.061] COLLECTION OF ELECTROSPUN POLYMER NANOFIBERS

Woraphon Kataphinan, Darrell H. Reneker (Maurice Morton Institute of Polymer Science, The University of Akron, Akron, Ohio 44325-3909)

The dry nanofibers produced in a typical electrospinning process are electrically charged. The nanofibers were directed by an electrical field, a tensile force along the axis of the fiber, and by the viscous drag force of moving air. The looping and spiraling path of the nanofibers, which resulted from bending and other kinds of instabilities that occurred as the fiber was formed, also complicated the collection process. Non-woven sheets of nanofibers were made by attracting the nanofibers to a conducting sheet or screen. The sheet or screen was flat and stationary, or wrapped around a rotating drum. Nanofibers were also collected in a liquid. The liquid removed charge or solvent. Nanofibers were collected on the surface of a non-wetting liquid, so that the patterns formed by the arriving nanofibers were observed directly. Streams of air, and air vortices were also used. These methods are being combined with robotic manipulators to collect nanofibers in many useful forms.

[L36.062] In situ x-ray scattering study of a main-chain thermotropic liquid crystalline polymer under oscillatory shear flow

Nitin Vaish, Wesley R. Burghardt (Northwestern University), Weijun Zhou, Julia A. Kornfield (California Institute of Technology)

Liquid crystalline polymers (LCPs) have been the subject of extensive studies because of potential commercial applications and scientific challenges. The excellent mechanical properties of LCPs arise from highly anisotropic molecular structure, which develops as a complex interplay between molecular dynamics and the applied flow field. We study the behavior of model thermotropic main-chain LCP (DHMS-7,9) under oscillatory shear flow using in situ X-ray scattering techniques. Experiments were done in nematic (140^o C) and x-phase (110^o C) to study the effects of frequency (0.5 - 50 rps) and strain amplitude (50 – 200In nematic phase, strong alignment in the flow direction (‘parallel’) was observed. The steady state was reached quickly either at high strain amplitudes or high frequencies. In x-phase, molecules aligned in flow direction at high strain levels or oscillation frequency, while alignment in vorticity (‘perpendicular’) direction was observed at low strain amplitude or frequency. In addition, we present the flipping of orientation from parallel to perpendicular alignment as a result of step change in temperature from 140^o C to 110^o C and oscillatory motion from a pre-aligned parallel state in x-phase.

[L36.063] Nucleation in Microcellular Thermoplastic Foams

Pieter Spitael, Christopher W. Macosko (Department of Chemical Engineering and Materials Science, University of Minnesota)

Amorphous, thermoplastic polymers are foamed using inert gases such as carbon dioxide or nitrogen to create a microcellular foam. The small cell size, smaller than critical flaws already present in most polymers, allows the microcellular foam to retain some critical mechanical properties present in the bulk material. Microcellular foams with a cell density greater than 10^8 cells/cm^3 and an average cell size of order 10 microns or less, have been succesfully produced in amorphous polymers such as polystyrene, poly(methyl methacrylate) and polycarbonate. Current processing methods make it difficult to achieve a high cell nucleation density. In an effort to control the cell nucleation density, heterogeneous nucleation sites, both solid particle sites and in the form of block copolymer micelles, have been added to polystyrene samples. Batch experiments using carbon dioxide gas reveal anomalous trends in nucleation behavior that can not be explained by the classical nucleation theory, prompting further inquiry into its validity.

[L36.064] Electrospun high performance nanofibers

Wenxia Liu, Zongquan Wu, Darrell H. Reneker (Maurice Morton Institute of Polymer Science, The University of Akron, Akron, Ohio 44325-3909)

Poly(meta-phenylene isophthalamide) was electrospun from solution to form nanofibers. The resulting nanofibers were birefringent and ranged in diameter from 30 to 300 nanometers. High-speed videographic observations showed that the jet developed the bending, looping and spiraling path characteristic of electrospinning. The thermal properties and the structure of the as-spun and annealed nanofibers were characterized by thermogravimetric analysis, X-ray diffraction and transmission electron microscopy. Both electron and X-ray diffraction patterns of the as-spun fibers showed diffuse equatorial diffraction spots, indicating that the molecules were oriented along the axis of the nanofiber. After annealing, the diffraction spots became much sharper, and other spots appeared, indicating that the as-spun fibers were in a metastable state. Nanofibers of this material were stable up to 200°C.

[L36.065] Flipping from the Perpendicular to Parallel Orientation in Block Copolymers: An Electron Microscopy Study

Lei Qiao, Karen Winey (Department of Materials Science and Engineering, University of Pennsylvania)

Previous studies in lamellar diblock copolymers have determined the processing conditions necessary to create the parallel and perpendicular orientations. In addition, studies have shown a flipping behavior between the perpendicular and parallel orientations. The purpose of this study is to investigate the mechanisms by which the flipping occurs. A low molecular weight styrene-isoprene diblock copolymer was first aligned in the perpendicular orientation through extensive large amplitude oscillatory shear. Flipping from the perpendicular to parallel orientation was then conducted and interrupted at intermediate stages. The evolution of the parallel orientation and the morphological development at these stages were characterized by the electron microscopy. Simultaneous shearing and small angle x-ray scattering were also performed to elucidate the flipping mechanism.

[L36.066] Processing Effects on Block-Copolymer–Based Pressure-Sensitive Adhesives

A. E. O'Connor, C. W. Macosko (University of Minnesota)

The goal of this work is to investigate how the variables in the hot-melt coating process affect the microstructure and properties of pressure-sensitive adhesives based on a styrene–isoprene–styrene triblock copolymer. This polymer is a thermoplastic elastomer, able to be coated at high temperatures and physically crosslinked at lower temperatures. Adhesive tape samples have been made through hot-melt and solvent coating methods. Hot-melt coatings are prepared at speeds up to 110 feet/minute. Materials with the same thermal history have been coated using both methods and then tested for comparison of properties. PSA properties are strongly dependent on the time scale of application and debonding, as revealed by shear rheology data, and three types of performance tests (tack, peel, and shear holding power) are used to capture the various responses. Solvent-coated tape has superior shear strength, while hot-melt-coated tape performs better in peel tests. It is expected that the varying flow and deformation histories of the samples will lead to distinct chain orientations, while the rate of cooling of hot-melt-coated samples may influence the degree of phase separation achieved. These factors will cause the adhesive coatings to have different microstructures and therefore different properties.

[L36.067] Achieving microkelvin control at room temperature

Amy L. Lytle, D.T. Jacobs (The College of Wooster, Wooster OH 44691)

An experiment is in progress to investigate the turbidity of a liquid-liquid mixture very close to its critical temperature. Temperature is controlled precisely through an onion-layer design, with successive stages of control and measurement. This process is automated using a program in LabVIEW, an icon-based programming language. Control of the temperature has been achieved to within a few microkelvin of the critical temperature, which is near room temperature. The techniques and methodology that allow such precise temperature control and measurement will be presented along with the results showing 10ppb control.

Acknowledgment is made to NSF-REU grant DMR 9619406 and to NASA grant NAG8-1433 for support of this research.

[L36.068] Roughening and De-roughening of the Interface Width in an Electrophoretic Deposition of Polymer Chains

Frank Bentrem, Ras B. Pandey (University of Southern Mississippi)

A discrete lattice of size L_x \times L_y \times L_z is considered with a large aspect ratio L_x/L_y(L_z). Polymer chains, each of length L_c are released from one end (x=0) of the sample in presence of a field (E) along x-direction. In addition to excluded volume, a nearest neighbor repulsive interaction is considered among the polymer nodes. Metropolis algorithm is used to move chain nodes: kink-jump dynamics is primarily used in this study, however, attempts are made to explore the effects of other dynamics such as crank-shaft and reptation. As the polymer density grows at/near the wall (x=L_x), an interface develops. Density and coformational profiles of the polymer chains and the interface width are monitored as function of Monte Carlo steps (MCS). Growth of the interface width (W) of the polymer density with time, i.e., W \sim t^ \beta, is analyzed in detail and the saturated width W_s = W, t \to \infty is evaluated as a function of temperature, field strength, and chain length. Using the scaling of the saturated width (W_s) with the transverse dimension, i.e., W_s \sim L_y(z)^\alpha, the roughness exponent \alpha is esimated. Variations of the interface width and the roughness exponent with the smulation parameters (E, T, L_c) exhibit interesting roghening and de-roughening phenomena, some of these results will be presented.

[L36.069] Pattern Coarsening of Spherical Copolymer Microdomains

Christopher Harrison, Zhengdong Cheng, Paul M. Chaikin, David A. Huse (Department of Physics), Richard A. Register (Department of Chemical Engineering), Douglas H. Adamson (Princeton Materials Institute, Princeton University)

We have investigated two dimensional pattern coarsening dynamics with a block copolymer which microphase separates into spheres. The system consisted of a single layer of polystyrene spheres in a polyethylene-alt-polypropylene matrix (PS-PEP) on a substrate and was studied by hot stage atomic force microscopy (AFM). By performing Delaunay triangulation, we quantitatively demonstrate a high density of free dislocations and a relatively low density of free disclinations. By obtaining sequential AFM images as a function of annealing time, we have tracked the grain growth and defect motion. During annealing, the correlation length saturates at temperature dependent values, resulting in pinned grain boundaries consisting of a high density of dislocations and disclinations. Increasing the annealing temperature decreases barriers to motion, depinning defects from grain boundaries and resulting in a better ordered pattern with fewer grain boundaries.

[L36.070] Simulation of a Liquid Crystal at an Amorphous Polymer Surface

T. P. Doerr, P. L. Taylor (Case Western Reserve University)

Atomistic molecular dynamics simulations of the anchoring of a liquid crystal at the surface of an amorphous polymer have been performed. The particular materials modeled were 5CB in the nematic phase at the surface of amorphous polyethylene. The inverted pendulum model of B. Lin and P. L. Taylor (Physics Letters A 172) (1993) 281-284 indicates that the dynamics of the substrate, in this case amorphous polyethylene, can stabilize non-planar orientations of the liquid crystal molecules. Simulations were performed to test this hypothesis. In order to isolate the effects of the motion of the polymer substrate on the liquid crystal, two sets of simulations were performed: in one set the atoms comprising the polyethylene were allowed to move and in the other set the polyethylene atoms were fixed. Also, simulations were performed starting from both planar and homeotropic initial conditions.

[L36.071] Structural Properties of a Two-Dimensional Coulomb System

Girija S. Dubey, Godfrey Gumbs (Hunter College/CUNY)

There is very keen interest from a thoretical as well as an experimental point of view to determine the initial conditions which one can use to predict the formation of a Wigner crystal in experiments. The density at which solids can be formed from individual particles is limited by the range of their interaction potential. Short-range forces can only bind particles at high density, whereas long-range forces, e.g. the Coulomb interaction, are capable of forming solids even at very low densities. Wigner predicted the existence of such a low-density Coulomb solid for electron systems, the so-called Wigner crystal. Recently, the experimental realization of a Wigner crystal was found in an electron system with charged calloidal particles in an aqueous solution, and charged dust particles in plasmas. Using numerical simulation, we demonstrate that there are several densities at which a Wigner crystal exists for the two dimensional electron gas.

[L36.072] Propagation of Heterogeneous Substrate Induced Ordering in Thick Block Copolymer Films

Lee D. Rockford, Thomas P. Russell (Umass Amherst, Dept. Polymer Science and Engineering), M. Yoon, S. G. J. Mochrie (Massachusetts Institute of Technology, Dept. Physics)

Commensurability of chemical and physical length scales between substrate heterogeneity and copolymer morphology has been shown to induce control over block copolymer ordering in thin films. In thicker films, free surface effects compete with substrate incuded ordering and prevent the oriented morphology from propagating throughout the entire film thickness. Herein we examine the crossover region between substrate control and free surface effects. Varying both film thickness and solvent casting under different conditions, as well as spin casting and annealing, we probe the effects of competing free surface and substrate control.

[L36.073] Modeling the Molecular Packing of Copper Phthalocyanine / Poly (1-lysine) Multilayer Thin Films

Angela L. Campbell (Air Force Research Laboratory, Materials & Manufacturing Directorate, AFRL/MLPJ, Wright-Patt AFB, OH 45433), D.R. Wiff (AFRL/MLPO)

A broadening research effort on how cation species affects association, structure, and packing of Copper Phthalocyanines (CuPcTs) in Electrostatic Self-Assembly (ESA) thin films is underway. Here we present molecular dynamics simulations using Cerius2 software to examine the CuPcT / Poly(1-lysine) molecular level deposition process. The shape of the CuPcT molecule and the chain conformations of the poly(1-lysine) molecule are examined. An amorphous glass slide is simulated and on this molecular layers of CuPcT and poly(1-lysine) are sequentially deposited. At each level the depositing molecule atoms are allowed full motion while the previously minimized layers atoms are fixed. A grand canonical ensemble minimization at 800K is followed by a minimization at 300K and finally one at 0K. After a deposited monolayer global conformation is minimized, the atoms in the top two layers are allowed to vary to obtain a local minimum at 0K. We find this modeling scheme to be very effective and final molecular spacings agree well with ellipsometry data.

[L36.074] Spinodal dewetting in polymer/polymer systems

A. M. Higgins, R. A. L. Jones (Department of Physics and Astronomy, University of Sheffield, Sheffield S3 7RH, UK), M. Sferrazza (ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, UK), P. Jukes, J. Sharp, L. Dryden (Department of Physics and Astronomy, University of Sheffield, Sheffield S3 7RH, UK), J. Webster (ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, UK)

In the spinodal dewetting process, a thin liquid film breaks up due to the unstable growth of capillary waves driven by dispersion forces across the film. We have investigated the dewetting of a polymer melt substrate by a polymer thin film. The dewetting of polystyrene (PS) by a thin poly(methyl methacrylate) (PMMA) film has been studied using optical microscopy, atomic force microscopy and neutron reflectivity. The characteristic length of the dewetted morphology has been investigated by changing the thickness of the bottom (PS) layer, which changes the effective Hamaker constant of the system. Changing the substrate from which the PMMA film was floated can control the degree of order in the dewetted morphology. The early stage kinetics of dewetting are followed by measuring the growth of the interface and surface roughness with neutron reflection. The kinetics are studied as a function of the molecular weight of the polymers and of temperature.

[L36.075] Novel method of tailoring the surface properties of elastic materials

Kirill Efimenko, Jan Genzer (NC State University, Raleigh, NC)

We present a novel method for controling the wetting properties of materials. Our technique is based on the grafting reaction between w(CH_2)_xSiCl_3 molecules and the surface -OH functionalities. A thin film made of a poly(dimethyl siloxane) (PDMS) network is first stretched and then physically modified to produce surfaces containing grafted -OH groups, which are used as attachment points for the chlorosilane molecules. The grafting density of the organic modifiers can be adjusted by controlling the strain on the PDMS substrate, \Deltax. We test the feasibility of the proposed grafting technique by attaching semifluorinated (SF) self-assembled monolayers (SAMs), F(CF_2)_y(CH_2)_xSiCl_3 (FyHx), to PDMS substrates. After the SAM deposition, the stress from the substrate is released and, as a result, the grafted FyHx chains form well-organized SAMs with an exceptional order of packing and alignment. The water contact angles (\theta) are found to increase with increasing the strain on the pristine PDMS substrate and reach values larger than \theta=130^o for \Deltax=50resistance of the SF-SAMs against water exposure is investigated. Experiments using scanning force microscopy on samples exposed to water reveal significant variations in the surface topography with the immersion time. However, near-edge X-ray absorption structure and water contact angle measurements indicate that regardless of the immersion time, the SF chains stay oriented and maintain their great wetting properties.

[L36.076] Mobility of polymer chains at the polymer/air interface

Tobias Kerle, Zhiqun Lin, Ho-Cheol Kim, Thomas P. Russell (University of Massachusetts, Amherst MA01003)

Relaxation of polymers from non-equilibrium conditions will in general only occur if the polymeric system is above the bulk glas temperature. The mobility of the chains near the solid surface can be, depending on the interaction with the surface, either enhanced or depressed. To examine the influence of a free surface on the mobility of polymer chains rough surfaces of thick polystyrene films (> 5 \mum) were prepared. Each peak or surface asperity of the PS film presents a non-equilibrium system with a large interfacial surface area. Depending on the mobility of chains the peaks will decay in order to minimize the overall surface area. Relaxation of the surface asperities at temperatures well below the bulk glas temperature is observed. One typically observes a fast decay of structures with a high aspect ratio and small lateral extension, leaving the surface with peaks of rather well defined aspect ratio and a lateral extension above a critical value. A second far slower process is observed with virtually no change of the aspect ratio.

[L36.077] Microstructure of a new Poly[(A-r-B)_x-b-B_y] (y>x) gradient copolymer

Zhiqun Lin, Thomas P. Russell (University of Massachusetts, Amherst, MA., 01003), Elbert E. Huang, Didier Benoit, Craig Hawker (IBM Almaden Research Center, San Jose, CA., 95120)

The morphology and structure of gradient copolymers of poly[(styrene-r-maleic anhydride)-b-polystyrene] were investigated. Reflection optical microscopy images showed continuous color changes at the edge of the spin-coated thin films indicating that a layering of the morphology parallel to the substrate interface did not occur. Microphase separation was observed by atomic force microscopy measurements on reactive ion etched samples, which showed cylindrical microdomains oriented normal to the surface. The cylinder-cylinder separation distance was about 16nm, consistent with bulk values determined by x-ray scattering. No interference maxima were seen in neutron reflectivity experiments over a temperature range from 130^oC to 190^oC, suggesting a vertical orientation of the cylinders. The surface tension of the gradient copolymer was slightly higher than that of PS. The combined control over the orientation of the microdomains with the ability to convert the anhydride to the corresponding acid makes the materials interesting candidates for functional nanascopic arrays.

[L36.078] Rheology of Confined Telechelic Chain under Shear

June Huh, Anna C. Balazs (Chemical and Petroleum Engineering, University of Pittsburgh)

We study rheologiacl behavior of di-end-functionalized polymer confined between two flat walls by using Monte Carlo simulation. In order to investigate the effect of the associating structure induced by functional groups on the rheological properties, we simulate three kind of telechelic chains with different number of associating capacity, f=1, 2 and 3 and compared the shear responses of these polymers. When the associating capacity of a functional group is larger than 1, physically crosslinked network of associating structure effectively blocks the extreme chain stretching against shear deformation, resulting in decrease of limiting shear stress.

[L36.079] Thickness dependence of the glass transition temperature in thin polymer films

Wang-Cheol Zin (Dept.of Material Science and Engineering, Pohang University of Science and Technology), Jae Hyun Kim, Jyongsik Jang (School of Chemical Engineering, Seoul National University)

The glass transition temperature of thin polymer film is studied in this work. We have used ellipsometry to measure the glass transition temperature(Tg) of poly(alpha-methyl styrene)[PAMS] thin films as functions of film thickness and molecular weight. When the films are thinner than a few hundreds of angstroms, substantial reduction in Tg is apparent and Tg of the film approaches the asymptotic value with increasing film thickness. Tg depression pattern of PAMS does not differ with molecular weights. To fit our experimentally obtained thickness dependent Tg data, the Michaelis-Menten equation, which is widely known model in enzyme kinetics, is analogized. The observed Tg depression data in thin film has the good agreement with our analogized equation and two adjustable parameters are obtained from fitting. The large surface to volume ratio in thin film geometry is the main reason for the Tg reduction in thin film.

[L36.080] Investigation of p-quaterphenyl layers vapor deposited on KCl (001) by Atomic Force Microscopy (AFM)

Jr. Kintzel, D.H. Van Winkle, J.G. Skofronick, S.A. Safron (Florida State University), F. Flaherty (Valdosta State University), D.-M. Smilgies (European Synchrotron Radiation Facility, France), Valdosta State University Collaboration, European Synchrotron Radiation Facility Collaboration

We have investigated the structural properties of the aromatic molecule p-quaterphenyl (p-4P) vapor deposited onto a KCl (001) surface at a pressure of 10^-6 mbars. In a series of AFM studies, thicknesses of p-quaterphenyl varying from 1 to 20 monolayers exhibited unusual features not previously imaged. Included in our observations are: i) needle-like accumulations of the p-quaterphenyl around surface defects, ii) a striped-phase region with a lateral spacing of approximately 25 nm for a nominal monolayer of p-4P, and iii) a thickness range where we found indications for a transition from lying to standing orientation of the molecules.

[L36.081] Interfaces of two immicible polymer thin films studied by X-ray Scattering

K. Shin, Y. Seo, M. Rafailovich, J. Sokolov (State University of New York at Stony Brook), H.O. Seeck, S.K. Sinha (Argonne National Laboratory), R. Jones, S. Kumar (Penn State University), R. Kolb (Exxon Research and Engineering Company)

We investigated the interface of PS/PMMA and PS/ PVP as a function of film thickness by X-ray scattering, SIMS and AFM techniques. Although the neutron scattering of two immiscible polymer/polymer interfaces has been investigated by Sferrazza et.al( PRL, 78, 1997), the disadvantages of small qz range(~0.15A^-1) and lower resolution of neutron reflectivity brought difficulties to detect within reasonable error range. By the way X-ray reflectivity can overcome these limitation of neutron reflectivity because of its much larger qz ranges and high resolution, but the small contrast, which is that most of polymers have very similar refractive index of X-ray, was only problem. Recently, we found that X-ray reflectivity can be analyzed using Fourier method (Seeck et al, APL, in preparation) to detect the ultra-small density contrasts in thin film layer system. Therefore with great advantages of X-ray scattering compared to neutron scattering, this method can be applied specially to polymer-polymer interfaces without any further contrast alteration. The results are showing that interfacial energy as well as film thickness are the most important factors to modify the intrinsic interfacial width and additional interfacial broadening by capillary wave. The results were well matched to the theoretical calculation within very small error ranges. Experiments are currently in progress for bilayer systems with diblock copolymer. The existence of diblock copolymer can reduce tremendously the interfacial tension of immcible polymer/polymer interface and bring the interfacial length broadening.

[L36.082] Surface Segregation of Fluorine in Thin Films of Poly (Methyl Methacrylate-co-Tetrahydroperfluorooctylacrylate) (PMMA/TAN) Random Copolymers.

Nora Beck Tan, Wendy Kosik, Joseph Deitzel, Steve McKnight (US Army Research Laboratory, Materials Division AMSRL-WM-MA, APG, MD 21005.), Stephanie Crette, Joseph DeSimone (Department of Chemistry University of North Carolina at Chapel Hill Chapel Hill, NC 27599-3290)

Design and control of polymer surface functionality is desirable for numerous applications. It is widely known that hydrophobic polymer surfaces can be produced on block-copolymers due to surface segregation of hydrophobic blocks. Less research has been performed on random copolymer compositions. In this work, we investigate the surface segregation of a series of random copolymers composed of methyl methacrylate (MMA) and tetrahyrdroperflourooctyl acrylate (TAN). Thin films (150-200 nm) were solution spun-cast onto silicon substrates. As deposited and samples annealed above the copolymer glass transition temperature were studied to assess the degree of surface reorganization that might occur. Surface analysis using water contact angle measurements and angle resolved XPS indicate that the concentration of fluoro groups increases near the surface of the film in all compositions. The degree of surface segregation was dependent on the PTAN to PMMA ratio of each copolymer. The segregation was enhanced after annealing the films at elevated temperatures.

[L36.083] Surface Segregation and Bulk Thermodynamics of Polybutadiene Star/Linear Blends

T. D. Martter, M. D. Foster, G. Lizarraga, S. Xu, R. P. Quirk (U. of Akron, Dept. of Polymer Science, Akron, OH 44325), P. Butler, C. F. Majkrzak (National Institute of Standards and Technology, Gaithersburg, MD 20899), J. D. Demaree (Army Research Lab, AMSRL-WM-ME, APG, MD 21005)

We investigated the effect of chain architecture on surface segregation and bulk thermodynamics of blends of well-defined star-branched and linear polybutadiene. Bulk thermodynamics were sensitively studied with Small Angle Neutron Scattering. The thermodynamic interaction parameter was found to increase with branching and also to vary somewhat with composition. The surface properties were studied with Neutron Reflectometry, and Nuclear Reaction Analysis. These measurements were performed on blends with varying compositions, number of arms of the star, and molecular weight of linear deuterated PB.

[L36.084] Diffusion Behavior in Metal/Polymer Nanocomposites

Rodney Guico (Northwestern University, Argonne National Laboratory), Kenneth Shull (Northwestern University), Jin Wang, Lynn Rehn, Peter Baldo (Argonne National Laboratory)

Characterizing diffusion behavior of metal nanoparticles in a polymer matrix is important for understanding metal/polymer interfacial dynamics. We have applied a variety of techniques to study such mobility in a gold/poly(tert-butyl acrylate) system in order to obtain a more complete picture of the diffusion behavior. X-ray standing wave along with reflectivity techniques were used to measure gold particle movement in a time resolved manner. Diffusion coefficients were also calculated from peak broadening in Rutherford backscattering spectrometry experiments. These methods were complemented by TEM, which shows the two-dimensional distribution of particles.

[L36.085] Effect of Strain on the adsorption of CO on Pd(100)

H. Metiu, M.W. Wu (Chemistry Department, University of California, Santa Barbara, CA 93106)

We present a density functional study of the adsorption of CO on the Pd(100) surface, to examine how surface strains affects adsorption isotherms. We find that the coverage, at a given temperature and presure, is changed substantially by strain.

[L36.086] Tuning the wetting behavior of block copolymers on self-assembled monolayers exposed to ionizing radiation

Richard Peters, Xiao Yang, Paul Nealey (Department of Chemical Engineering, University of Wisconsin)

Exposure of self-assembled monolayers to x-ray and extreme ultra violet radiation in the presence of air or oxygen results in the incorporation of oxygenated functional groups on the surface of the monolayer. The extent of chemical modification was determined as a function of dose and oxygen concentration. Dewetting, symmetric, neutral and asymmetric wetting of poly(styrene-b-methylmethacrylate) thin films was observed with increasing concentration of oxygenated functional groups. The results were analyzed using the Fowkes-van Oss-Chaudhury-Good approach for determining solid/liquid interfacial tensions. We will discuss and demonstrate applications of this technique to tune the surface properties of substrates for nanopatterning and to induce macroscopic ordering of thin films of diblock copolymers.

[L36.087] Symmetric Diblock Copolymer Thin Films Confined Between Two Hard Surfaces: Simulations and Theory

Qiliang Yan, Qiang Wang, Paul Nealey, Juan de Pablo (Department of Chemical Engineering, University of Wisconsin-Madison)

The morphology of thin films of symmetric diblock copolymers confined between two hard and flat surfaces was explored by means of Monte Carlo simulations on a lattice. For such simulations, the match between the bulk lamellar period and the simulation box size is crucial to obtain meaningful results. The simulations were performed in an expanded grand-canonical ensemble, where the chemical potential and the temperature of the confined film were specified and its density was allowed to fluctuate. Our simulations have revealed various types of morphology, depending on the surface configurations.

To construct the phase diagram for confined thin films, we have combined the results of simulations with a phenomenological theory. The simulations provide valuable insights into the lowest free-energy morphologies that are required by the theory; these structures are sometimes difficult to guess by simple intuition. The theory is useful for rationalizing the simulation results and for designing experimental protocols that will permit long-range patterning of nanoscale features.

[L36.088] Phase transition of LB films of mixed diblock copolymer at the air/water interface

Y.S. Seo, K.S Kim, V. Samuilov, M.H. Rafailovich, J. Sokolov, Rob G.H. Lammertink, G.J. Vancso (Affiliation)

We have studied the morphology of Langmuir blodgett films at the air/water interface of mixed diblock copolymer films. Solutions of poly(styrene-b-ferrocenyldimethylsilane) and PS-b-P2VP mixed in a ratio of 20/80 in chloroform were spread at the air/water interface. The morphology of the films was studied with AFM as a function of the surface pressure and the diblock copolymer molecular weight. The results show that the two diblock copolymers can be induced to mix at the air/water interface with increasing surface pressure. A reversible transition from spherical to cylindrical morphologies is induced in the mixture which can not be observed in films formed of the two components separately. The effective surface phase diagram as a function of block copolymer composition and pressure will be presented.

[L36.089] Brushes and Mushrooms in Diblock Copolymer/Homopolymer Mixtures

Andreas Terzis, Doros N. Theodorou, Chris Toprakcioglu (Univ. of Patras and FO.R.T.H.-I.C.E./H.T., Greece), Haralambos Retsos, Spiros H. Anastasiadis (FO.R.T.H.-I.E.S.L. and Univ. of Crete, Greece), Greg Smith (LANSCE, Los Alamos), Alain Menelle (C.E.N. Saclay, France), Yves Gallot (Inst. Charles Sadron, France), Georges Hadziioannou (Groningen, Univ., The Netherlands)

The interfacial segregation of block copolymers to the substrate/polymer interfaces from their mixtures with the respective homopolymers in thin films is investigated by neutron reflectivity and lattice-based self-consistent mean-field calculations; the adsorbed chain configuration was probed as a function of the ratio of block lengths. The segment density profiles of either PV2P-PS or PMMA-PS diblocks adsorbed at the PS/substrate interface are evaluated. Both experiment and theory reveal evidence for a broad transition from a "mushroom" to a "wet brush" configuration of the dangling chains by changing the ratio of the block lengths.

[L36.090] Anisotropic Buckling in a Confining Coverlayer Directs Island and Hole Formation in an Underlying Lamellar Block Copolymer Thin Film

M. R. Hammond, G. H. Fredrickson, E. J. Kramer (UCSB)

We cast symmetric poly(styrene-b-2vinylpyridine) (PS-PVP) diblock copolymer thin films on Si which form lamellae oriented parallel to the substrate surface, with equilibrium thicknesses 1.5 L_0, 2.5 L_0, etc, where L_0 is the equilibrium lamellar period. We investigate films of initial thickness 2.0 L_0, which form bicontinuous domain structures (1.5 or 2.5 L_0 thick) after annealing. If a thick, glassy confining film is placed on top of the block copolymer film before annealing, island and hole formation is restricted and the underlying lamellar morphology is forced to reorganize, whereas a thinner, elastically deformable confining layer will buckle to accommodate island and hole growth in the underlying film. By creating confining films with controlled topologies, we show that island and hole growth can be oriented, with domains forming parallel to directions of minimum bending stiffness of the cover layer topological structure.

[L36.091] Long-Range Order of Symmetric Block Copolymer Thin Films

Ho-Cheol Kim, Thomas Russell (Polymer Science and Engineering Department, University of Massachusetts at Amherst)

The long-range lateral ordering of the lamellar microdomains of symmetric diblock copolymers of styrene and methyl methacrylate was studied. Thin films of the block copolymer were prepared by spin coating solutions of the copolymer onto a nonpreferential surface which was made by end grafting poly(styrene-r-methyl methacrylate) random copolymer having a styrene fraction of 0.58 to silicon substrates. In the case of very thin films the nonfavorable interactions with the substrate result in a dewetting. The contact line is found to pin fluctuations, laterally, leading to a long-range lateral ordering of the lamellae that extends microns across the surface. The evolution and interfacial interactions dependence of the alignment will be addressed.

[L36.092] Controlling the Long Range Ordering of Block Copolymer Micelle Films

R.A. Segalman, H. Yokoyama, E.J. Kramer (UCSB)

The surfaces of polymer thin films preferentially attract one block of a diblock copolymer and this attraction can induce layering of spherical microdomains of asymmetric poly(styrene-b-2vinylpyridine)(PS-PVP) diblock copolymers, resulting in long range order perpendicular to the surface. We demonstrate that the lateral structure of such an asymmetric diblock copolymer film may be controlled by imposing a topological pattern on the film surface, resulting in a perfectly packed hexagonal array in 2-D, i.e., with no grain boundaries and few, if any dislocations. We observe the structure of these films by sputtering down to the midplane of a layer of PVP spheres with the oxygen ion beam of a secondary ion mass spectrometer and then imaging the exposed surface by scanning force microscopy. These images show that the topologically confined stripe of copolymer is ordered in a single crystalline, close packed structure with hexagonal symmetry for stripe widths as wide as 4 \mums, with a definite epitaxial orientation relationship between the edges of the stripe and the close packed directions in the layer. Such control may prove useful in lithographic applications of block copolymer films.

[L36.093] Alignment mechanisms of diblock copolymers in electric fields

Jason DeRouchey (UMass-Amherst Polymer Science and Engineering), Thomas Thurn-Albrecht, Tom Russell (UMass-Amherst), Sushil Satija (NIST)

Precise control of the orientation of block copolymer domains is of interest for the production of self-assembling nanoporous media. Electric fields are effective in orienting copolymer domains normal to a surface. In thin films of poly(styrene-block-methyl methacrylate), a threshold electric field strength E_t was found, which for film thicknesses greater than 10 \mum, was independent of film thickness and could be described by the difference in interfacial energies of the diblock components with the substrate. Neutron reflectivity, small angle neutron and x-ray scattering and off-specular scattering suggest that interfacial fluctuations are amplified by the electric field that leads to orientation of the cylinders along the field lines. In the case of poly(styrene-block-isoprene), a material with a smaller difference in dielectric constants, the microdomain orientation occurs at higher field strengths. Also the reorientation process is more rapid than in poly(styrene-block-methyl methacrylate).

[L36.094] Fracture of interfaces between glassy polymers in a trilayer geometry

Nicolas Passade, Costantino Creton (Laboratoire PCSM-ESPCI, Paris, FRANCE)

We have investigated the fracture behavior of A/B/A assemblies where A is a thick (2mm) beam of a glassy polymer and B is a thin (1 to 200 microns) layer of another glassy polymer immiscible with A. The external loading, the molecular structure at the A/B interface and the thickness of the B central layer were varied and the fracture toughness Gc was measured for each assembly. Fracture always occurred at one of the A/B interfaces and the microscopic deformation mechanisms depended on the molecular structure at the interface, on the plastic deformation properties of the A and B polymers but also on the thermal residual stresses in the layer and on the degree of mode mixity ahead of the crack tip, which was imposed by the external loading. A significant amount of shear stresses at the interface promoted the formation of oblique crazes in one of the two polymers and this caused a surprising dependence of Gc on the layer thickness which will be discussed. http://umr7615.pcsm.espci.fr/^\simpassade/gb/indexgb.html

[L36.095] The Relationship of Pretilt Angle and Chemical Structure of Rubbed Organo-Soluble Side-Chain Polyimides

Ian K. Mann, F. Bai, Z. Bai, J. Ge, L. Sun, H. Wang, Z. Zhang, Frank W. Harris, Stephen Z.D. Cheng (Maurice Morton Institute and Department of Polymer Science, The University of Akron, Akron, OH 44325-3909)

This work is concerned with the relationship between the properties of the pretilt angles and chemical structure of the alignment layer for a series of novel organo-soluble side-chain polyimides developed at The University of Akron. The polyimides were spin cast on ITO glass substrates and mechanically rubbed with a velvet cloth. Liquid crystal display cells were constructed with an anti-parallel geometry using 10\mum glass spacers and filled with the nematic liquid crystal mixture E7. The pretilt angle, which is defined as the angle between the liquid crystal director and the substrate, was measured using the magnetic null method. Various side-chain polyimide films were prepared and pretilt angles were determined employing identical processing conditions. In general, polyimides containing long flexible aliphatic side-chains (no. carbons >12) resulted in high pretilt angles (>20^o) however over time the pretilt shifted to a homeotropic alignment (i.e. 90^o to the substrate). The stability of the pretilt angles was improved when polyimide copolymers were used. Further enhancement of the stability was achieved by crosslinking the system prior to rubbing. Liquid crystal like side-chains (cyanobiphenol and biphenol based) resulted in stable pretilt angles ranging from 20 to 40^o for a spacer length of six carbons. Several surface techniques were used to study the effect of rubbing, including; atomic force microscopy, surfaced enhanced Raman scattering, and contact angle.

[L36.096] Reactive Processing with Difunctional Oligomers to Increase Interfacial Adhesion in Polymer Blends

Charles O'Brien, Kevin Rice+, Mark Dadmun (The University of Tennnessee, Knoxville)

The intoduction of blocky copolymers represents a possible method of compatibilizing two immiscible polymers in a blend. However, copolymers do not diffuse quickly to the interface of a polymer blend system. Therefore, reactive processing is being investigated as a means to form in-situ compatibilizers for polymer blends. A model system composed of poly(bisphenol A-co-epichlorohydrin) blended with poly(ethylene oxide) that is compatibilized with difunctional oligomers that are the same structure as the blend components is currently under investigation. It is expected that the oligomers can undergo an addition copolymerization during processing to create the blocky copolymers at the biphasic interface. Initial tensile measurements show that the addition of the reactive oligomers improves the properties of the blend. Additionally, preliminary results indicate that reactive oligomers may act as plasticizers and continue to polymerize at room temperature after the blend is removed from the melt mixer if insufficiently mixed.

[L36.097] Fracture Toughness of Modified Poly(ethylene terephthalate)/Gelatin Interfaces

B.Y. Asoo, E.J. Kramer (UCSB), C.-A. Dai (Eastman Kodak)

The poor wettability of gelatin solutions on nonpolar poly(ethylene terephthalate) (PET) and subsequent inadequate adhesion of cast gelatin films to PET substrates, can be improved by modifying the surface of the PET. Plasma treatment of the PET, which creates reactive surface functional groups, is a suitable surface modification. We measure the fracture toughness, G_c, of a semi-crystalline poly(ethylene terephthalate)/gelatin interface using an asymmetric double cantilever beam (ADCB) technique as a function of sample thickness, relative humidity, and plasma parameters. The results indicate that varying the thicknesses of the two beams, and thus the mechanical phase angle, is important to control the direction of crack propagation. Under high relative humidity G_c increases due to water absorption and plasticization of the gelatin. The fracture toughness increases as the product of the plasma power and exposure time of the PET to the plasma.

[L36.098] Experimental and theoretical investigation of random copolymer segregation

W Li, B Tang, Y Zhang, D Gersappe, M Rafailovich, J Sokolov (Department of Materials Science and Engineering, SUNY, Stony Brook, NY 11794), D Peiffer, M Lin (Exxon Research and Engineering, Annandale, NJ 08851), J A Dias, K O MacElrath (Exxon Chemical Corp, Bayton, TX 77520)

In this work we will show the compatibilization effect of random copolymer AB in homopolymer A and random terpolymer CDE rubbery system. In particular, we studied the interfacial property of styrene-butadiene rubber (SBR) in the interface of polybutadiene(PB) and functionalized polyisobutylene (Brominated isobutylene-co-methylstyrene, BIMS). Neutron reflectivity (NR) results indicated that BIMS/PB interfacial width broadened significantly (from 4nm to over 30nm) with the addition of SBR in PB. Flory-Huggins parameters were obtained from interfacial width of BIMS/PB and BIMS/SBR profiles measured with NR. Flory-Huggins parameter for SBR/PB was obtained from literature. With three Flory-Huggins parameters available, the interfacial property of SBR was studied with SCF (Self-Consistent Field) modeling. SCF modeling will be compared with NR results.

[L36.099] Numerical Investigation of Monodisperse Polymer in an Athermal Solution Between Two Surfaces

Matthew Yi, Mukesh Chhajer, P. D. Gujrati (University of Akron, Akron OH 44325)

We investigate a monodisperse polymer in an athermal solution between two surfaces, through a numerical method developed by Chhajer and Gujrati which has been successfully applied to a polydisperse system. The monodisperse polymers require distinguishing a monomer by its distance from the end-point, which was not the case with the polydisperse polymers. Previously, we have applied this method to fixed length polymer lengths and explored effects next to a surface and bulk properties. We replace the original cubic lattice by a modified tree structure of the same coordination number. This modification allows us to capture some of the correlations produced by the surface. The model is then solved by recursive technique. Here we report our results for a system of fixed length polymers between two surfaces of finite separation. We report the results of our computation of various density profiles as a function of the distance between the two surfaces. We also present results for the surface entropy and the surface free energy as a function of surface interaction energy as well as the effect of chain length.

[L36.100] Structure Within Thin Epoxy Films Revealed by Solvent Swelling: A Neutron Reflectivity Study

Hyun Yim, Michael Kent, W. Frere McNamara (Sandia National Laboratories), Robert Ivkov, Sushil Satija (NIST), Jaroslaw Majewski (Los Alamos National Labs)

Structure within thin epoxy films is investigated by neutron reflectivity (NR) as a function of resin/crosslinker composition and cure temperature. Variation in the crosslink density normal to the substrate surface is examined by swelling the films with the good solvent d-nitrobenzene (d-NB). The principal observation is a large excess of d-NB near the air surface. This is not a wetting layer, but rather indicates a lower crosslink density in the near-surface region. This effect is due to preferential segregation of the crosslinker to the air surface, driven by the lower surface tension of the crosslinker relative to the epoxide oligamers. The magnitude of the effect is a function of composition and cure temperature. Exclusion of d-NB from the region immediately adjacent to the substrate surface is also observed, possibly indicating a tightly bound layer of epoxy. Regarding swelling in the bulk of the films, the behavior is nonsymmetric with departure from the stoichiometric ratio. The films deficient in curing agent show greater equilibrium swelling and faster swelling kinetics than the films with an excess of curing agent.

[L36.101] Interdiffusion of Polyethylenes in Microlayers

Sergei Nazarenko, Eugene Stepanov, Anne Hiltner, Eric Baer (Case Western Reserve University, Department of Macromolecular Science,Center for Applied Polymer Reserach)

Kinetics of interdiffusion of a miscible polymer pair, high density polyethylene (HDPE) and linear low density polyethylene (LLDPE), was studied experimentally and theoretically in order to characterize the conditions required to construct micro- and nanoscopic gradient morphologies from microlayers. Microlayers were taken into the melt for a period of time, and the compositional gradient was fixed by crystallization upon quenching. High specific interfacial area of microlayers offset the low diffusion mobility of polymeric chains so that the microlayer in the melt approached composititional homogeneity on a laboratory time scale. The progress of interdiffusion was analyzed by thermal behavior, optical, electron and atomic force microscopy. The analysis revealed the role of different fractions and heterogeneity in the chain microstructure, and allowed us to extract the diffusion coefficients for elementary chains in the developing melt blend from the net kinetics of interdiffusion. It was found that the interlayer boundaries remained stationary during a characteristic time of interdiffusion of the component main fractions, and moved at long times as high molecular weight fractions became involved in interdiffusion. Interdiffusion of polyethylene pairs in microlayers was exploited to increase the concentration of inorganic particles in one of the components. When microlayers of LLDPE and low density polyethylene (LDPE) were taken into the melt, significantly greater mobility of linear LLDPE chains compared to branched LDPE chains caused a significant shrinkage of LLDPE layers. Adding a particulate in the LLDPE did not impede the process of interdiffusion in the melt, and the resultant shrinkage served to increase the particle concentration.

[L36.102] Patterning of a Semicrystalline Block Copolymer Thin Film via Epitaxial Crystallization

Cheolmin Park (Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139), Claudio De Rosa (Dipartimento di Chimica, Universita'di Napoli "Federico II" Via Mezzocannone 4, 80134 Napoli, Italy), Lewis J. Fetters (Exxon Research and Engineering Company, Annandale, New Jersey 08801), Bernard Lotz (Centre de Recherches sur les Macromolecules, CNRS Strasbourg, 67083 France), Edwin L. Thomas (Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139)

Epitaxial crystallization of a semicrystalline block copolymer onto a crystalline organic substrate guides microphase pattern formation. We used a semicrystalline triblock copolymer composed of a crystallizable polyethylene (PE) block, a glassy polystyrene block (PS) and a rubbery mid-block of alternating ethylene and propylene units (PEP). The surface interaction between the crystallizable PE block and the crystalline organic substrate induces a well ordered vertical lamellar structure of the crystalline block, within which polymer chains are epitaxially oriented, as evidenced by bright field imaging as well as selected area electron diffraction. The oriented pattern of the crystalline PE induced by the crystallographic epitaxy with the anthracene substrate simultaneously creates a layering of the PS component. Such control will be useful for the patterning of the block copolymers from the Angstrom to the micron scale.

[L36.103] Size induced glass transition in ultra-thin films and its impact in diffusive and elastic behavior.

J. Andres Torres, David S. Fryer, Paul F. Nealey, Juan J. de Pablo (UW-Madison)

Experiments show that ultra thin free-standing polymeric films have a lower glass transition temperature (Tg) than that of the bulk, but a higher Tg when supported on strongly attractive substrates. Our Tg values obtained by ellipsometry and local probe calorimetry are fully consistent. Molecular simulations of such films indicate the existence of two regions in the films: a low mobility region near strongly attractive substrates, and a high mobility region near a free surface. High mobility induces a lower Tg while low mobility tends to increase it. To understand the mechanisms behind these changes, self-diffusion coefficients were determined in bulk, supported and free-standing films. Tg changes could have serious implications for nanolithography. Simulations of structure deformation explored the changes that can be expected in the mechanical properties of nano scale structures. The results indicate that the Young's modulus of a polymeric material undergoes tremendous changes in the sub-100 nanometer range and feature's aspect ratio, temperature, and substrate's characteristics influence its elastic behavior.

[L36.104] Understanding the morphology and dynamics of ordering of thin films of diblock copolymers on chemically heterogeneous surfaces

Xiao Yang, Richard Peters, Qiang Wang, Juan dePablo, Paul Nealey (Department of Chemical Engineering, University of Wisconsin)

Chemically heterogeneous surfaces patterned with length scales from 10s of microns to 10s of nanometers were used as substrates for thin films of symmetric poly(styrene-b-methylmethacrylate). Film morphology was described by alternating regions of symmetric/asymmetric wetting or symmetric/neutral wetting, and patterns formed in the films due to differences in thickness between different wetting regions. Evidence of mass transport of polymer molecules on the surface of the films was observed. Pattern features coarsened with annealing time, film surfaces were smooth over one region even when the film thickness did not equal the quantized thickness for the type of wetting present in that region, and perpendicular lamellae were present at the free surface on patterned films over regions with neutral wetting. Some of the results were analyzed using a combination of Monte Carlo simulations and theory.

[L36.105] Thermal Expansion Behavior of Thin Polycarbonate Films

Christopher Soles, Wen-li Wu (NIST Polymers Division)

Recently the issue of physical property deviations in ultra-thin polymer films has received considerable attention in the literature. However, the majority of these works primarily focus on PS and PMMA, two polymers with very high entanglement molecular weights. In this work, we extend the thin film studies to polycarbonate, a polymer with one of the lowest entanglement molecular weights. Polycarbonate films of variable thickness are spun coat onto Si wafers and the thermal expansion is observed with specular X-ray reflectivity. For films supported on a wafer with the native oxide of Si, the expansion behavior is very bulk-like for thicknesses greater than 100 ÅFor films thinner than 100 Å\/ (the rms end-to-end length is ~ 160 Åthe apparent glass transition appears to be depressed. In these same sub-100 Å\/ films, a negative coefficient of thermal expansion is observed for temperatures below about 80 ^\circC. Curiously, this negative coefficient of thermal expansion is no longer observed when the sub-100 Å\/ films are supported on a hydrogen passivated Si wafer, suggesting that substrate interactions are important. The origins of these phenomena are to be discussed in greater detail.

[L36.106] Molecular dynamics