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At least 91 records · Page 5

Extreme Ultraviolet and Beyond Extreme Ultraviolet Lithography Using Amorphous Zeolitic Imidazolate Resists Deposited by Atomic/Molecular Layer Deposition

Amorphous zinc-imidazolate (aZnMIm) resists show potential to meet the demands for next-generation high-numerical aperture (high-NA) metal-containing extreme ultraviolet (EUV) resist materials, given their ease of deposition by atomic/molecular layer deposition (ALD/MLD) at thicknesses of 20 nm and below. Here, this study demonstrates that aZnMIm thin films, previously identified as high-resolution electron beam resists, can also function as negative-tone EUV photoresists. Water development achieves high sensitivity (5 mJ/cm 2 ) but leaves significant residue, while acetic acid development results in poor contrast. A hybrid approach─water followed by acetic acid─enables residue-free development with a sensitivity of 181 mJ/cm 2 . Dry development using 1,1,1,5,5,5-hexafluoroacetylacetone (hfacH) is also possible but shows lower sensitivity (375 mJ/cm 2 ) compared to wet development methods. EUV photoelectron spectroscopy (PES), reflectometry/EUV absorption, total electron yield (TEY), residual gas analysis (RGA), and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were used to investigate the effects of EUV irradiation on aZnMIm resists. Reflectometry experiments reveal an aZnMIm EUV absorption coefficient of 6.2 μm –1 , while PES and TEY analyses show that, compared to poly(4-hydroxystyrene) (PHS), a polymer-based reference resist, aZnMIm emits more primary and secondary electrons but generates fewer slow electrons relative to its primary electron emission; its total electron yield is similar to that of poly(methyl methacrylate) (PMMA) resists. When exposed to EUV, aZnMIm predominantly outgasses H 2 , as determined by RGA. TOF-SIMS measurements demonstrate that high-dose EUV exposure only partially fragments the 2-methylimidazole (2MIm) organic linkers, unlike high-dose electron beam exposure, which is known to completely degrade them. Additionally, aZnMIm resists show promise for potential beyond EUV lithography (BEUVL) due to the presence of Zn, which provides higher sensitivity at a wavelength of 6.7 nm compared to other metal ions, such as Sn, that are currently used in the best-performing EUV metal–organic resists. TEY measurements demonstrate that aZnMIm emits nearly twice as many electrons as PHS at 6.7 nm. The BEUV TEY of aZnMIm also surpasses that of PMMA, poly(pentafluorostyrene), and poly(4-iodostyrene), with the latter two being known for their high EUV TEYs. This work provides insight into zeolitic imidazolate framework (ZIF)-based EUV and BEUV resists and highlights their potential for both wet and dry development.

lithography↗

Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Rapid and reliable processing methods for forming ordered block copolymer (BCP) materials with low defect density in a thin film geometry are required for many nanotechnology applications. Vertically aligned BCP structures, in particular, have applications ranging from nanolithography for electronics and photonics to nanoporous membranes for water remediation and novel batteries for flexible electronics. However, the attainment of nearly complete vertical orientational order of the BCP ordered phase remains challenging. Solvent-based techniques, such as direct immersion annealing (DIA) and solvent vapor annealing (SVA), have immense potential for these applications of BCP films, as it allows for tuning of their thermodynamic, structural, and chain mobility driven kinetic properties. We first demonstrate that DIA, using a judicious choice of binary solvent mixtures along with a relatively hydrophobic ionic liquid (IL), induces the rapid vertical ordering in polystyrene-b-polymethylmethacrylate (PS-PMMA) block copolymer in lamellar films. The IL establishes synergy to the binary solvent mixture of toluene and heptane to 1 create a near-neutral solvent environment for attaining the vertical microstructure of the BCP. Next, we show that IL can suppress the de-wetting of the PS-PMMA films to achieve long-range order using SVA in cylindrical films for long annealing times. Both vertical and horizontal morphology is attained in these films by selecting different solvent environments. Furthermore, attaining enhanced vertical and horizontal BCP structure with long-range defect-free order by tuning solvent quality and using additives like IL can render them useful for many nanotech applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of the Interfacial Energy between Graphene Nanoplatelets and Deuterated or Hydrogenated Polystyrene

The tracer diffusion coefficients of various graphene nanoplatelet-polystyrene (GNP-PS) systems were determined by using dynamic secondary ion mass spectrometry, which provided insights into the interactions within the polymer nanocomposite system. Bilayer films, where one contained trace amounts of deuterated polystyrene (dPS), were produced, and the interdiffusion was measured by detecting the position of the dPS interface. GNPs were placed in both or only one of the two layers. The diffusion coefficient was decreased when GNPs were present in both layers as compared to the samples without GNP, indicating an attractive interaction between GNP and polystyrene. Surprisingly, the coefficient increased relative to the control when GNPs were present only in the PS containing layer, whereas it decreased most strongly when GNP and dPS were present only in the same layer, indicating that an additional preference existed for GNPs and dPS. A significant difference in interfacial energies was measured using contact angle goniometry of PS or dPS droplets on flat GNP layers, confirming the preferential interaction. DFT calculations were used to calculate the interfacial interaction between GNP and dPS or PS, and they showed an attractive potential which was maximal when the PS rings were conformal with the GNP structure. Furthermore, the differential energy between PS and dPS at the GNP interface was in excellent agreement with the measured value. In contrast, contact angle goniometry indicated that the interaction between GNP and poly(methyl methacrylate) (PMMA) was unfavorable, and no difference in interfacial energy between dPMMA and PMMA was observed. Therefore, these techniques can provide a means for determining the relative affinity between GNP and different polymer hosts, which can be an important consideration in the mechanics and adhesion properties of the compounds.

36 MATERIALS SCIENCE↗

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗

Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns

Here, nanopatterning for the fabrication of optical metasurfaces entails a need for high-resolution approaches like electron beam lithography that cannot be readily scaled beyond prototyping demonstrations. Block copolymer thin film self-assembly offers an attractive alternative for producing periodic nanopatterns across large areas, yet the pattern feature sizes are fixed by the polymer molecular weight and composition. Here, a general strategy is reported that overcomes the limitation of fixed feature size by treating the copolymer thin film as a hierarchical resist, in which the nanoscale pattern motif is defined by self-assembly. Feature sizes can then be tuned by thermal reflow controlled locally by irradiative crosslinking or chemical alteration using lithographic ultraviolet light or electron beam exposure. Using blends of polystyrene-block-poly(methylmethacrylate) (PS-b-PMMA) with PS and PMMA homopolymer, we demonstrate both self-assembled PS grating and hexagonal hole patterns; exposure-controlled reflow is then used to reduce hole diameter by as much as 50% or increase PS grating linewidth by more than 180%. Transferring these nanopatterns, or their inverse obtained by a lift-off approach, into silicon yields structural colors that may be prescriptively controlled based on nanoscale feature size. Furthermore, patterned exposure enables area-selective feature size control, yielding uniform structural color patterns across centimeter square areas. Electron beam lithography is also used to show that the lithographic resolution of this selective-area control can be extended to the nanoscale dimensions of the self-assembled features. The exposure-controlled reflow approach demonstrated here takes a pivotal step towards fabricating complex, hierarchical optical metasurfaces using scalable self-assembly methods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Polycaprolactone: A Promising Addition to the Sequential Infiltration Synthesis Polymer Family Identified through In Situ Infrared Spectroscopy

Infiltration of inorganic oxides inside polymers using sequential infiltration synthesis (SIS) is an effective method for creating materials for a broad range of applications. The reactions between various polymer functional groups and organometallic/inorganic precursors are unique, which makes it essential to understand the specific interactions for a range of precursors and polymers to enable predictive process design and to extend the utility of SIS to applications. In this paper, in situ Fourier transform infrared spectroscopy (FTIR) measurements have been performed during Al 2 O 3 and TiO 2 SIS in three different homopolymers: poly(methyl methacrylate) (PMMA), poly(epsilon-caprolactone) (PCL), and poly(2-vinylpyridine) (P2VP). From the FTIR intensity changes after precursor exposure and during the subsequent purge times, it is demonstrated quantitatively that the interaction dynamics and the stability of the intermediate complexes of these polymers with the metal precursors are substantially different. A key finding from this comparative study is that PCL interacts far more strongly with metal precursors, even though its carbonyl (C=O) and ester (C-O-R) functional groups are similar to those of the more weakly interacting PMMA. This behavior suggests that additional factors beyond the identity of the functional groups dictate how polymers interact with metal compounds in SIS. PCL, which has not previously been reported in SIS processes, may be an attractive polymeric template for implementing SIS with improved uniformity and cost-effectiveness.

36 MATERIALS SCIENCE↗

Resolving the Atomic Structure of Sequential Infiltration Synthesis Derived Inorganic Clusters

Sequential infiltration synthesis (SIS) is a route to the precision deposition of inorganic solids in analogy to atomic layer deposition but occurs within (vs upon) a soft material template. SIS has enabled exquisite nanoscale morphological complexity in various oxides through selective nucleation in block copolymers templates. However, the earliest stages of SIS growth remain unresolved, including the atomic structure of nuclei and the evolution of local coordination environments, before and after polymer template removal. We employed In K-edge extended X-ray absorption fine structure and atomic pair distribution function analysis of high-energy X-ray scattering to unravel (1) the structural evolution of InO x H y clusters inside a poly(methyl methacrylate) (PMMA) host matrix and (2) the formation of porous In 2 O 3 solids (obtained after annealing) as a function of SIS cycle number. Early SIS cycles result in InO x H y cluster growth with high aspect ratio, followed by the formation of a three-dimensional network with additional SIS cycles. That the atomic structures of the InO x H y clusters can be modeled as multinuclear clusters with bonding patterns related to those in In 2 O 3 and In(OH) 3 crystal structures suggests that SIS may be an efficient route to 3D arrays of discrete-atom-number clusters. As a result, annealing the mixed inorganic/polymer films in air removes the PMMA template and consolidates the as-grown clusters into cubic In 2 O 3 nanocrystals with structural details that also depend on SIS cycle number.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hyperspectral and Nanosecond Temporal Resolution Widefield Infrared Photothermal Heterodyne Imaging

Label-free, bond-selective imaging offers new opportunities for fundamental and applied studies in chemistry, biology, and materials science. Preventing its broader application to investigating spectrally congested specimens are issues related to low sensitivity as well as low spatial and temporal resolution. Here, we demonstrate a widefield, mid-infrared (MIR) photothermal imaging technique, called widefield Infrared Photothermal Heterodyne imaging (wIR-PHI), that massively parallelizes acquisition of MIR absorption data through use of a high-speed complementary metal-oxide-semiconductor camera. wIR-PHI possesses notable features that include: spatial resolution significantly below the MIR diffraction limit, hyperspectral imaging capabilities, high sensitivity, and ~100 ns temporal resolution. Here, the first two features are highlighted by hyperspectral imaging of proximally close poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanoparticles where clear, bond-specific imaging of nanoparticles, separated by less than the MIR diffraction limit, is demonstrated. Sensitivity is highlighted by imaging individual PMMA and PS nanoparticles with radii between r = 97-556 nm. This leads to a current, peak absorption cross-section limit-of-detection of σ abs = 1.9× 10 –16 cm 2 . wIR-PHI's 100 ns temporal resolution is simultaneously demonstrated by observing the decay of photothermal contrast on individual nanoparticles on a ~200-6000 ns timescale. In whole, wIR-PHI’s dramatic increase in acquisition speed opens opportunities for future MIR kinetic imaging and spectroscopic studies of important chemical, biological, and material processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A study of degradation mechanisms in PVDF-based photovoltaic backsheets

Abstract Commercial backsheets based on polyvinylidene fluoride (PVDF) can experience premature field failures in the form of outer layer cracking. This work seeks to provide a better understanding of the changes in material properties that lead to crack formation and find appropriate accelerated tests to replicate them. The PVDF-based backsheet outer layer can have a different structure and composition, and is often blended with a poly(methyl methacrylate) (PMMA) polymer. We observed depletion of PMMA upon aging with sequential (MAST) and combined (C-AST) accelerated stress testing. In field-aged samples from Arizona and India, where PVDF crystallizes in its predominant α-phase, the degree of crystallinity greatly increased. MAST and C-AST protocols were, to some extent, able to replicate the increase in crystallinity seen in PVDF after ~ 7 years in the field, but no single-stress test condition (UV, damp heat, thermal cycling) resulted in significant changes in the material properties. The MAST regimen used here was too extreme to produce realistic degradation, but the test was useful in discovering weaknesses of the particular PVDF-based outer layer structure studied. No excessive β-phase formation was observed after aging with any test condition; however, the presence of β-phase was identified locally by Fourier transform infrared spectroscopy (FTIR). We conclude that both MAST and C-AST are relevant tests for screening outdoor failure mechanisms in PVDF backsheets, as they were successful in producing material degradation that led to cracking.

14 SOLAR ENERGY↗

Understanding the unique optical and vibrational signatures of sequential infiltration synthesis derived indium oxyhydroxide clusters for CO 2 absorption

Sequential infiltration synthesis (SIS) is a vapor phase synthesis technique with potential to exert precise control over metal oxyhydroxide incorporation into polymer scaffolds. Here, we observe strong size-dependent properties of InO x (OH) y few-atom clusters deposited with variable SIS cycle numbers within a polymethylmethacrylate (PMMA) matrix. Infrared spectroscopy and ultraviolet-visible absorption spectroscopy reveal that the metal atom coordination and optical properties of the clusters depend on the number of SIS cycles performed as well as the choice of processing parameters. The incorporation of indium oxyhydroxide in PMMA via SIS presents an opportunity to improve the CO 2 absorption capacity and gas selectivity of inexpensive polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infiltration synthesis of hybrid nanocomposite resists for advanced nanolithography

In this work, we demonstrate a simple ex-situ inorganic infiltration route for transforming standard organic resists into highperformance positive tone hybrid resist platform. A model thin film PMMA-AlOx hybrid resist system has been synthesized by hybridization of PMMA with AlOx and investigated for electron beam lithography. The approach possesses full controllability of the resist performance in terms of critical does, patterning contrast reaching up to 30 and etch resistance for plasma-based pattern transfer processes. The high selectivity Si etching capability demonstrated using a lowtemperature cryo-Si etch process, based on the controlled infiltration outperforms commercial resists and typical hard mask material thermal SiO 2 , with estimated achievable selectivity in excess of ~300. Si nanostructures down to ~30 nm with aspect ratio up to ~17 are also transferred into the Si substrate. Easy implementation and adaptability for different inorganic infiltrations, this platform is well capable of potentially delivering the resist performance and throughput necessary for EUV lithography.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

IER 480: TEX-Pu Benchmark (PU-MET-THERM-004) to Test Polyethylene and Lucite Thermal Scattering Laws [Slides]

This presentation finds that PMT-004 has four new benchmark cases highly sensitive to PE TSL (2 cases) and PMMA TSL (2 Cases). PE cases were well predicted using MCNP6.2 and ENDF/B-VIII.0. PMMA cases overpredicted by approximately 0.6-0.7% in k eff at 20°C. Accepted into 2023 version of the ICSBEP Handbook. Temperature had a large impact on reactivity of the critical configuration. Implications for validation work for thermal cases- need to adjust TSL data to correct temperature as it can have hundreds of pcm effects for a few °C. Future thermal experiments should try and measure reactivity at multiple temperatures to aid in data testing and benchmark adjustment.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Evaluation of Engineered Form MOFs CaSDB and HKUST-1

Idaho National Laboratory (INL) and Pacific Northwest National Laboratory (PNNL) have studied different sorbents for the purpose of separating krypton (Kr) and xenon (Xe). PNNL has researched various metal-organic frameworks (MOFs) that have characteristics theoretically suitable for the separation. Based on computational analysis, PNNL chose Calcium–4,4’–sulfonyl dibenzoate (CaSDB) and Hong Kong University of Science and Technology MOF1 (HKUST–1). The raw MOFs are supplied in a powder form and must be incorporated into a robust engineered form to be viable for gas separation. In 2016, PNNL produced an engineered form of CaSDB by compressing and grinding the raw MOF material. This form was sent to INL for adsorption testing. Gentle mechanical agitation of the compressed form produced a large amount of powder, resulting in the conclusion that the form was not viable for the application. In 2019, INL successfully produced two engineered forms, CaSDB–EF1 and HKUST–EF2, by incorporating the active MOF powders into a polyacrylonitrile (PAN) binder. PNNL also produced two engineered forms, CaSDB–10pmma and HKUST–10pmma, by using polymethyl methacrylate (PMMA) as a binder. Surface area analysis indicated that the forms could be viable for separations in which the CaSDB–EF1 retained 84% of the raw CaSDB surface area and CaSDB–10pmma retained 48%. HKUST–EF2 retained all the raw HKUST–1 surface area, whereas HKUST–10pmma retained only 28%. Mechanical stability testing demonstrated that the PMMA forms formed a fine powder whereas, the PAN forms did not. In general, adsorption testing showed that CaSDB–10pmma had a lower Xe breakthrough capacity than CaSDB–EF1, but a higher saturation capacity at both room temperature and at 253 K. The CaSDB MOF was intended to be used as a room temperature sorbent to capture Xe. However, both CaSDB engineered forms displayed relatively short initial break through times. Reduced temperature increased the Xe capacity of both engineered forms. HKUST–1 was expected to be effective only at sub-zero temperatures. At 195 K, HKUST–10pmma had an initial Xe breakthrough capacity of 119 mmol/ kg, compared to HKUST–EF2 at 339 mmol/ kg. The saturation capacities were 275 and 383 mmol/ kg, respectively. HKUST–10ppm also had a lower Kr capacity of 1.7 mmol/kg, whereas the HKUST–EF had a Kr capacity of 3 mmol/ kg. Test results indicate that the PAN engineered forms are a more suitable choice for the complete separation of Xe and Kr, due to the increase in initial breakthrough capacity. CaSDB allows rapid breakthrough of Kr and Xe regardless of the type of engineered form. At 253 K, it is more viable, but is still not the most effective sorbent. HKUST–EF2 demonstrated viability for Xe capture at 195 K, which may merit further study, however it may be cost prohibitive.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Viscoelastic Damping and Wave Cutoff of Titanium Alloy and Lattices

Here, the 3D-printed titanium alloy Ti5553 solid and octet truss lattice specimens are studied via resonant ultrasound spectroscopy, free decay of vibration and quasi-static methods to determine viscoelastic damping. Damping in solid alloy and a lattice is between 10 -4 and 10 -3 . Much of the damping at high sonic frequency is attributed to stress-induced heat flow between heterogeneities due to 3D printing. Pulsed wave ultrasound experiments disclose reverberation in the cell structure of the lattice. Continuous wave ultrasound experiments show that the transmissibility in the lattice rolls off beginning at about 50 kHz and becomes negligible above 110 kHz. By contrast, the polymer polymethyl methacrylate (PMMA), though it is viscoelastic, readily transmits waves up to 1 MHz. The cutoff frequency in the lattice is associated with the structure size, not intrinsic damping in the alloy. The octet truss lattice, in addition to providing good mechanical performance, is also an ultrasonic metamaterial.

36 MATERIALS SCIENCE↗

ATRP Enhances Structural Correlations In Polymerization–Induced Phase Separation**

Synthetic methods to control the structure of materials at sub–micron scales are typically based on the self–assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano– and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase–separated poly–methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous Degradation‐Depolymerization of Bioderived Comb Copolymers

Poly(lactic acid) (PLA) is the most widely explored biodegradable alternative for polystyrene; however, its low toughness and glass transition temperature may limit its wider adoption as a sustainable replacement. To improve its material and thermal properties, PLA can be chemically or physically combined with other polymers, like poly(methyl methacrylate) (PMMA), though the incorporation of vinyl‐based polymer components complicates chemical recycling and reduces the sustainability of the material. Here, in this study, we synthesized polymethacrylate‐PLA comb copolymers designed to be thermally deconstructed. Our design strategically extends current polymer deconstruction methodologies to more complex macromolecular systems. Thermally labile units within the polymethacrylate backbone permitted depolymerization that was concurrent with PLA side chain degradation during heating. This dual degradation‐depolymerization process enhances the overall sustainability of lactide/vinyl‐based copolymers and demonstrates the synergistic potential of integrating multiple deconstruction pathways into a single system. This report elaborates on the design of advanced, degradable copolymers, contributing to the further development of sustainable polymer materials.

PLA↗

The effects of electrically exploding gold bridgewires into inert and explosive powder beds

Abstract The particle velocity created in beds of both low-density inert sugar and explosive PETN as a function of distance from an exploding bridgewire was measured using optical velocimetry and a silvered PMMA window. As expected, more violent bridge-bursts (from a greater-stored-energy capacitive discharge unit) resulted in greater particle velocities and a better supported compaction wave in sugar. In all cases, ramp waves, not shocks, were observed in the inert sugar. Large window velocities were observed for very powerful bursts (up to 270 m/s), but bursts required for stochastic detonator operation conditions resulted in sugar/PMMA window velocities of only 8–10 m/s 0.85 mm from the bridge location. In contrast, after a distance of only 0.65 mm, a building shock wave was observed in PETN under both threshold and reliable firing conditions. Subsequently a hot-spot-driven shock-to-detonation (SDT) process was observed prior to full detonation. The measured buildup process accounts for $$\approx $$ ≈ 66% of the so-called excess transit time (ETT) between the observed and theoretical total function time for the particular exploding-bridge-wire (EBW) detonator studied. The remainder must occur in the powerful output pellet region. In contrast to a common understanding, the ETT is found to be a weak function of the discharge energy. Thus, the operation of the detonator after a bridge-burst energy-to-powder reaction transition process is found to be hot-spot-driven SDT in both the low- and high-density pellets.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Theoretical estimates of flammability bounds for thin condensed fuel diffusion flames in microgravity using detailed models of chemistry and radiation

Recently, U-shape flammability maps have been constructed showing minimal oxygen vs. flame strain for opposed flame spread in micro-gravity by Olson and Ferkul. The U-shape defines the limiting flammability bounds from radiative extinction and flame blow-off. Here, the minimum of the U corresponds to the minimum possible oxidizer concentration where burning can occur, and is an important quantity of interest for fire safety. While high strain extinction bounds have been well analyzed, low strain radiative extinction has not. To estimate low strain extinction, in this study an analytical theory is developed based on thin flame theory coupled with a heat and mass transfer model for solid fuels. A reaction progress variable based on the Damköhler number is adapted in the theory to account for incomplete combustion at high strain rates and enable the capturing of the full flammability map. The analytical model is compared to a one dimensional numerical model w/ detailed chemical kinetics and coupled radiation heat transfer in planar and spherical geometries. The flammability maps are then qualitatively compared to experimental extinguishment data compiled by Olson and Ferkul for cylindrical rods of PMMA showing similar trends. The results show the newly developed analytics capture the radiative extinction bound compared to the numerical model and qualitatively agrees with microgravity data.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗