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At least 901 records · Page 50

Quantifying molecular deformation in polymer melts by a generalized Zimm plot approach

The Zimm plot has been widely used to characterize the molecular dimensions of polymers from small-angle scattering experiments, where the reciprocal intensity is analyzed as a function of the square of the magnitude of the scattering wavevector Q. Here, this work explores the benefits of analyzing the reciprocal scattering intensity from deformed polymers, extending the original Zimm plot to anisotropic materials. In the small-angle limit, a tensorial extension of the Guinier law is found for the gyration tensor and the reciprocal single-chain structure factor. In the high-Q limit, application of the spherical harmonic expansion technique to the reciprocal structure factor permits direct model-independent analysis of spatially dependent molecular deformation of polymers. Additionally, the contributions from high-order spherical harmonics become insignificant in the reciprocal-intensity representation. The proposed generalized Zimm plot approach is demonstrated computationally with the affine deformation model and the Rouse model, and experimentally with small-angle neutron scattering measurements of deformed polystyrene melts.

36 MATERIALS SCIENCE↗

First experimental feasibility study of VIPIC: a custom-made detector for X-ray speckle measurements

The Vertically Integrated Photon Imaging Chip (VIPIC) was custom-designed for X-ray photon correlation spectroscopy, an application in which occupancy per pixel is low but high time resolution is needed. VIPIC operates in a sparsified streaming mode in which each detected photon is immediately read out as a time- and position-stamped event. This event stream can be fed directly to an autocorrelation engine or accumulated to form a conventional image. The detector only delivers non-zero data (sparsified readout), greatly reducing the communications overhead typical of conventional frame-oriented detectors such as charge-coupled devices or conventional hybrid pixel detectors. This feature allows continuous acquisition of data with timescales from microseconds to hours. In this work VIPIC has been used to measure X-ray photon correlation spectroscopy data on polystyrene latex nano-colliodal suspensions in glycerol and on colloidal suspensions of silica spheres in water. Relaxation times of the nano-colloids have been measured for different temperatures. These results demonstrate that VIPIC can operate continuously in the microsecond time frame, while at the same time probing longer timescales.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Polymer thin films as universal substrates for extreme ultraviolet absorption spectroscopy of molecular transition metal complexes

Polystyrene and polyvinyl chloride thin films are explored as sample supports for extreme ultraviolet (XUV) spectroscopy of molecular transition metal complexes. Thin polymer films prepared by slip-coating are flat and smooth, and transmit much more XUV light than silicon nitride windows. Analytes can be directly cast onto the polymer surface or co-deposited within it. The M-edge XANES spectra (40–90 eV) of eight archetypal transition metal complexes (M = Mn, Fe, Co, Ni) are presented to demonstrate the versatility of this method. The films are suitable for pump/probe transient absorption spectroscopy, as shown by the excited-state spectra of Fe(bpy) 3 2+ in two different polymer supports.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Magnetization Reversal of Three-Dimensional Nickel Anti-Sphere Arrays

Three-dimensional antisphere arrays (3DAAs) of Ni have been fabricated here using electrochemical deposition into self-assembled polystyrene sphere templates, which offers the advantage of straightforward scalability. Using the first-order reversal curve (FORC) method, the magnetic reversal mechanism is identified from the characteristic features in the FORC distribution. A left-bending boomerang-like feature is observed in the thinnest sample, which transforms to a ridge oriented along the local coercivity H c axis with increasing sample thickness. This transformation identifies a change in the reversal process from an exchange dominated domain-growth reversal to a localized weakly interacting particle-like reversal. Micromagnetic simulations confirm the decrease in domain growth and increase of pinning behaviors as the thickness of the Ni 3DAAs structure increases, providing strong support to the FORC analysis and interpretation.

36 MATERIALS SCIENCE↗

Microwave Sensing of Yeast Cell Species and Viability

We report the development of a simple interferometer-based microwave sensing system for multiple frequency characterization and differentiation of in-flow yeast cells. The interferometer uses a simple microstrip line, integrated with a microfluidic channel, for single-cell measurement. An algorithm was developed and verified with high-frequency structure simulator (HFSS) for complex permittivity, ε*( f ) = ε'( f ) - jε"(f), extraction from measured scattering parameters. The sensing system and the algorithm were evaluated by measuring polystyrene particles of different diameters and at different interferometer operating frequencies. Viable and nonviable Saccharomyces cerevisiae and Saccharomyces pastorianus cells were measured at those frequencies. The results showed frequency-dependent permittivity values for each species of yeast and viability as well as frequency-dependent permittivity differences between different yeast types. The differences at some frequency points are significant and enable the differentiation of cells in mixed suspension, which is also demonstrated with a prediction model developed in this work.

59 BASIC BIOLOGICAL SCIENCES↗

Production of Vanillin From Ferulic Acid by Pseudomonas putida KT2440 Using Metabolic Engineering and In Situ Product Recovery

Vanillin is the most in-demand flavouring compound in the world and because vanillin extracted from vanilla pods cannot meet the global demand, most vanillin on the market today is chemically synthesised. Increasing demands by consumers for natural ingredients have inspired efforts to develop vanillin derived from microbial sources. These efforts have been challenged by low titers, likely caused by the toxicity of vanillin to most microbial biocatalysts. In this study, we engineered a Pseudomonas putida KT2440-derived strain that accumulated vanillin from ferulic acid to 0.64 g/L. To increase the overall titre, we applied a hydrophobic polystyrene-based resin to vanillin-accumulating cultures, which enabled an increase in total vanillin recovery to an apparent titre of 3.35 g/L. This study demonstrates that P. putida can accumulate vanillin from ferulic acid to higher titers when vanillin is removed from the cultivation medium, mitigating its toxicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Monte-Carlo Method for Evaluating the Economic Performance of Plastics Recycling Systems Using Historical Pricing

The management of plastic waste is a considerable emerging global concern. Conventional plastics recycling rates range from 5–10% in the US, which results in considerable material being sent to landfill. New sorting technologies using artificial intelligence have the potential to dramatically increase the ability of waste management companies to sort out valuable fractions of plastic waste and create high-purity streams for secondary markets. However, several fractions of the plastics recycling stream, i.e., low-density polyethylene, polypropylene, and polystyrene, do not have well-developed markets. These materials may be sent to pyrolysis facilities for thermal recycling, but the economics of the pyrolysis industry are currently uncertain. This work aims to identify the breakeven price of the plastic fractions that would be sent to pyrolysis in order to determine the economic viability of the sorting facility. The work will use Monte Carlo analysis to evaluate several scenarios and understand how compositional variation, price variability, and facility attributes affect the breakeven price. Here, the presorting conditions in Materials Recovery Facilities strongly affects the profitability of the sorting facility. High residual high density polyethylene (HDPE) and polyethylene terephthalate (PET) content in presorted bales are important revenue drivers for the facility, even in presorted 3-7 bales. Key variables that lead to profitability include a high sale price of polyethylene terephthalate, a high sale price of high-density polyethylene, and if polypropylene can be sold to recycling markets (as opposed to pyrolysis facilities).

Plastics↗

Fabrication of nanoporous membranes for tuning microbial interactions and biochemical reactions

Here we describe how new strategies for combining conventional photo- and soft- lithographic techniques with high-resolution patterning and etching strategies are needed in order to produce multi-scale fluidic platforms that address the full range of functional scales seen in complex biological and chemical systems. The smallest resolution required for an application often dictates the fabrication method used. Micromachining and micro-powder blasting yield higher throughput, but lack the resolution needed to fully address biological and chemical systems at the cellular and molecular scales. In contrast, techniques such as electron beam lithography or nanoimprinting allow nanoscale resolution, but are traditionally considered costly and slow. Other techniques such as photolithography or soft lithography have characteristics between these extremes. Combining these techniques to fabricate multi-scale or hybrid fluidics allows fundamental biological and chemical questions can be answered. In this study, a combination of photolithography and electron beam lithography are used to produce two multi-scale fluidic devices that incorporate porous membranes into complex fluidic networks to control the flow of energy, information, and materials in chemical form. In the first device, materials and energy were used to support chemical reactions. A nanoporous membrane fabricated with e-beam lithography separates two parallel, serpentine channels. Photolithography was used to write microfluidic channels around the membrane. The pores were written at 150nm and reduced in size with silicon dioxide deposition from plasma enhanced chemical vapor deposition (PECVD) and atomic layer deposition (ALD). Using this method, the molecular weight cutoff (MWCO) of the membrane can be adapted to the system of interest. In the second approach, photolithography was used to fabricate 200nm thin pores. The pores confined microbes and allowed energy replenishment from a media perfusion channel. The same device can be used for study of intercellular communication via the secretion and uptake of signal molecules. Pore size was tested with 750nm fluorescent polystyrene beads and fluorescein dye. The 200nm PDMS pores were shown to be robust enough to hold 750nm beads while under pressure, but allow fluorescein to diffuse across the barrier. Further testing showed that extended culture of bacteria within the chambers was possible. Finally, these two examples show how lithographically defined porous membranes can be adapted to two unique situations and used to tune the flow of chemical energy, materials, and information within a microfluidic network.

36 MATERIALS SCIENCE↗

Effect of water vapor on plasma processing at atmospheric pressure: polymer etching and surface modification by an Ar/H 2 O plasma jet

In this study, we evaluate the effect of water vapor on the plasma processing of materials using a model system consisting of a well-characterized radio-frequency (RF) plasma jet, controlled gaseous environment, and polystyrene (PS) as target material. We find that the effluent of Ar/H 2 O plasma jet is capable of (1) etching polymers with relatively high etch rate and (2) weakly oxidizing the etched polymer surface by forming O containing moieties. When increasing the treatment distance between the polymer and the Ar/H 2 O plasma, we find that the polymer etch rate drops exponentially whereas the O elemental composition of the etched surface shows a maximum at intermediate treatment distance. The OH density in the Ar/H 2 O jet was measured near the substrate surface by laser induced fluorescence (LIF), and the density change of the OH radicals with treatment distance is found to be consistent with the exponential decrease of polymer etch rate, which indicates that OH may play a dominant role in the polymer etching process. A control experiment of Ar/H 2 plasma shows that the observed fast polymer etching by Ar/H 2 O plasma cannot be attributed to H atoms. By correlating the OH flux with the polymer etch rate, we estimated the etching reaction coefficient (number of C atoms removed per OH radical from the gas phase) of OH radicals as ~10 -2 . The polymer etch rate of Ar/H 2 O plasma is enhanced as the substrate temperature is lowered, which can be explained by the enhanced surface adsorption of gas phase species. For the same molecular admixture concentration and plasma power, we find that Ar/H 2 O/O 2 plasma has much reduced etching efficiency compared to either Ar/H 2 O or Ar/O 2 plasma.

36 MATERIALS SCIENCE↗

Si content in methacrylamide-containing A- b -(B- r -C) block copolymers and its impact on reactive ion etching properties

Block copolymers (BCPs) of an A-block-(B-random-C) architecture have been explored as materials for nanolithography because the composition and chemistry of the random block enables modification of thermodynamic and wetting properties to meet manufacturing criteria. Here, in this study, A-b-(B-r-C) BCPs created by an amidation reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with controlled amounts of Si add insight to previous conclusions about the dual contributions of BCP chemistry and reactive ion etch (RIE) gas chemistry on etch properties. We focus on two RIE etch characteristics: organosilicon etch resistance in H 2 /N 2 plasma etching and enhanced removal of non-styrenic structures in an Ar/O 2 etch. Consistent with previous studies, higher amounts of Si result in greater etch resistance under H 2 /N 2 RIE, where at least ∼10 wt. % Si is necessary to exhibit sufficient etch resistance. By contrast, Ar/O 2 etching resulted in etch rates independent of Si content. We observe previously unreported surface roughening aligned with morphological domains during the H 2 /N 2 etch of modified PS-b-PPFMA BCPs. Limited in the amount of allowable Si to attain equal surface energy between blocks, these BCPs are further disqualified in forming a Si-containing mask. However, in an Ar/O 2 etch, the same BCPs exhibit suitable etch contrast and smooth domain structures, forming a uniform PS mask. Ultimately, this study uses the chemical flexibility of these materials to demonstrate the mechanisms of interactions between BCP and etch chemistry that must be considered to design effective materials for pattern transfer applications.

Eom, Christopher J. [University of Chicago, IL (Un↗

Orientation control of high-χ triblock copolymer for sub-10 nm patterning using fluorine-containing polymeric additives

Directed self-assembly (DSA) of block copolymers (BCPs) Is one of the most promising techniques to tackle the ever-increasing demand for subllthographic features In semiconductor industries. BCPs with high Flory-Huggins parameter (chi) are of particular Interest due to their ability to self-assemble at the length scale of sub-10 nm. However, such high-chi BCPs typically have imbalanced surface energies between respective blocks, making it a challenge to achieve desired perpendicular orientation. To address this challenge, we mixed a fluorine-containing polymeric additive with poly(2-vlnylpyrldine)-block-polystyrene-block-poly(2-vlnylpyrldine) (P2VP-b-PS-b-P2VP) and successfully controlled the orientation of the high-chi triblock copolymer. The additive selectively mixes with P2VP block through hydrogen bonding and can reduce the dissimilarity of surface energies between PS and P2VP blocks. After optimizing additive dose and annealing conditions, desired perpendicular orientation formed upon simple thermal annealing. We further demonstrated DSA of this material system with five times density multiplication and a half-pitch as small as 8.5 nm. This material system Is also amenable to sequential Infiltration synthesis treatment to selectively grow metal oxide In P2VP domains, which can facilitate the subsequent pattern transfer. We believe that this integration-friendly DSA platform using simple thermal annealing holds the great potential for sub-10 nm nanopatterning applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic approach to defect reduction in directed self-assembly

As a potential solution to next-generation nanolithography, directed self-assembly (DSA) of block copolymers (BCPs) is still restrained in high-volume manufacturing primarily due to its defectivity issue. Though defects possess greater free energies than aligned morphologies and are highly energetically unfavorable, they can be kinetically trapped by the energy barriers and persist for a long time during annealing. Therefore, understanding the kinetics of defect annihilation is crucial in revealing the mechanism of defect formation and in further reducing defectivity in DSA. We focus on two types of predominant defects in DSA- dislocation and bridge. Furthermore, a kinetic model of each defect type is developed through statistical analysis of experimental data, providing insight into possible approaches of further defect reduction. We also investigate the impact of annealing temperature and film thickness on annihilation kinetics and discuss the reasons behind the observed results. By simply optimizing annealing conditions and film thickness, we have successfully reduced the total defect density by 1 order of magnitude. Though these findings are based on polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA), we anticipate they could be readily applied to other BCP platforms as well.

42 ENGINEERING↗

Effect of pattern transfer process on roughness of block copolymer patterns from directed self-assembly

Block copolymer-directed self-assembly (DSA) remains promising for improving pattern quality and reducing the stochastic variations that challenge high numerical aperture extreme ultraviolet lithography. Equally critical is refining pattern transfer methods for accurately transferring the rectified DSA features to the underlying substrate. We compare two atomic layer deposition (ALD)-based techniques: sequential infiltration synthesis (SIS) and dry liftoff, applied to polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DSA patterns. Both methods utilize aluminum oxide hard masks, with one synthesized through infiltration into the PMMA domains and the other through conformal ALD coating. High-resolution scanning electron micrographs were analyzed to measure line edge, width, and placement roughness for both the line (PMMA) and space (PS) features. Although both methods yielded similar overall 3σ rms roughness, they differed significantly in the frequency-dependent power spectral density (PSD) profiles. SIS reduced line placement roughness at length scales associated with the polymer pitch, but increased space width roughness at low frequencies, whereas dry liftoff mimicked the frequency content of the original guiding pattern. This study underscores the importance of PSD evaluation in selecting optimal pattern transfer strategies for specific applications.

Block copolymers↗

Multiresonant layered plasmonic films

Multi-resonant nanoplasmonic films have numerous applications in areas such as nonlinear optics, sensing, and tamper indication. While techniques such as focused ion beam milling and electron beam lithography can produce high-quality multi-resonant films, these techniques are expensive, serial processes that are difficult to scale at the manufacturing level. Here, we present the fabrication of multi-resonant nanoplasmonic films using a layered stacking technique. Periodically-spaced gold nanocup substrates were fabricated using self-assembled polystyrene nanospheres followed by oxygen plasma etching and metal deposition via magnetron sputter coating. By adjusting etch parameters and initial nanosphere size, it was possible to achieve an optical response ranging from the visible to the near-infrared. Singly resonant, flexible films were first made by performing peel-off using an adhesive-coated polyolefin film. Through stacking layers of the nanofilm, we demonstrate fabrication of multi-resonant films at a fraction of the cost and effort as compared to top-down lithographic techniques.

nano↗

Identification of contamination in the pulse-compression chamber of the OMEGA EP Laser System originating from clean room garments

The contamination of optical components with microscopic particles strongly impacts their ability to handle high-power or high-intensity laser pulses via an array of mechanisms. This work explores the nature and origin of a subset of contamination particles found inside the pulse-compression chamber of the OMEGA EP Laser System. Using Raman microscopy accompanied by other analytical methods, it was shown that sodium nitrate constitutes a significant fraction of the particles that possess diameters on the order of a few micrometers. Further investigation aiming to reveal the origin of these particles suggests that these sodium nitrate particles are deposited via shedding from the reusable clean room garments worn in the Laser Bay and compression chamber. Raman microscopy also revealed various plastic particles such as polystyrene, polyethylene, and poly(diallyl isophthalate).

Raman spectroscopy↗

Nanofabrication and inspection of fuel capsules for inertial confinement fusion

3D nanofabrication via Two-Photon Polymerization (TPP) provides a unique capability of flexibly fabricating complex structures over 1D-3D dimensions and µm-cm scales with resolutions below 100 nm. In the past years, the Laser-Assisted Nano Engineering (LANE) Group at the University of Nebraska-Lincoln (UNL) has been working closely with the Laboratory of Laser Energetics (LLE) in developing practical TPP approaches to fabricating various target structures for Inertial Confinement Fusion (ICF). At the same time, fuel capsules for ICF experiments should be inspected for surface and wall-embedded defects. Plastics materials [e.g., for example polystyrene (PS)] are the common materials used to make fuel capsules. However, during their manufacturing, capsules usually contain defects (vacuoles) embedded inside the shell walls, which may distort the implosion processes and influence the ICF performance of the capsules. The size of vacuoles is usually in a range from 100 to 2000 nm. Coherent anti-Stokes Raman scattering (CARS) microscope offers the capabilities of inspecting and characterizing the capsule defects. Furthermore, cryo-CARS microscopy was developed to explore how fuel isotope distributed inside target when icing that could not be diagnosed before.

36 MATERIALS SCIENCE↗

Characterization of ablator dynamics initiated by picket-pulse conditions

Direct-drive laser-fusion targets may include low-cost plastic ablator material. Here, this work describes a tabletop experimental system designed to enable the investigation of the interaction of such ablator material as a function of the laser wavelength and the associated excitation mechanism. This experimental system offers time-resolved imaging of the material response with subpicosecond temporal resolution and ≈1-μm spatial resolution. The system involves synchronized femtosecond and picosecond lasers to initiate and characterize the dynamics of polystyrene planar targets irradiated by conditions similar to a “picket” prepulse from a direct-drive pulse shape. Ultrafast imaging of the initial excitation process followed by the resulting critical plasma formation, shock-wave propagation, and blowoff plasma expansion is used to compare the impact of excitation wavelength, 355 nm or 266 nm, on the ensuing dynamics. This work aims to investigate fundamental laser material interactions to help advance physics models that can inform the development of laser driver and target designs.

42 ENGINEERING↗

SU-E-T-240: Monte Carlo Modelling of SMC Proton Nozzles Using TOPAS

Purpose: To simulate the 60Co beam from a novel Gamma—Tomo SBRT system and to calculate the output factors and dose rates for different source configurations and collimator sizes. Methods: The BEAM-Monte Carlo code is used to realistically model the system geometry, including 32 source capsules, source housing, primary collimator and 4 different changeable collimators. The sources (6.22 mm of diameter) are located in 2 rows with different angles and distances to the longitudinal axis and the beams can be collimated to obtain four different circular field sizes at the isocenter (35 mm, 16 mm, 7mm, and 3.5mm). Since the dose distributions will be determined in a spherical polystyrene phantom of 8cm radius centered at the isocenter, a new geometry module is designed for the dose calculation. Results: : The caracteristics of the particle spectra emerging from each source are determined and the influence of the source position on the spectra reaching the isocenter is found to be minimal (<2%). We found that the scattered photons represent about 15% of the total number of photons reaching the scoring plane immediately (1 mm) below the source and primary collimator. The radial photon fluence does not vary significantly inside the collimator opening and decreases quickly beyond the 3cm radius (projected at the isocenter plane). Conclusion: Our preliminary results indicate that the position of the source and primary collimator assembly does not affect the energy spectra and fluence distributions reaching the isocenter significantly. This allows the use of a well-represented source model for all the sources to perform the dose calculations for all the changeable collimators for this novel Gamma-Tomo SBRT system.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗