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NASA NTRS1977

Heat exchanger-ingot casting/slicing process, phase 1: Silicon sheet growth development for the large area silicon sheet task of the low cost silicon solar array project

A controlled growth, heat-flow and cool-down process is described that yielded silicon with a high degree of single crystallinity. Even when the seed melted out, very large grains formed. Solar cell samples made from cast material yielded conversion efficiency of over 9%. Representative characterizations of grown silicon demonstrated a dislocation density of less than 100/sq cm and a minority carrier diffusion length of 31 micron. The source of silicon carbide in silicon ingots was identified to be from graphite retainers in contact with silica crucibles. Higher growth rates were achieved with the use of a graphite plug at the bottom of the silica crucible.

Schmid, F.↗

DOE OSTI2021

Alkaline salt-promoted construction of hydrophilic and nitrogen deficient graphitic carbon nitride with highly improved photocatalytic efficiency

Graphitic carbon nitride (g-C 3 N 4 ) possesses fascinating merits, but its practical applications are limited by the inferior properties of limited visible-light sorption, rapid recombination of photo-excited charge carriers and low electrical conductivity. Introduction of N-defects is an efficient approach to tune its optical properties, but strategies capable of creating abundant vacancies and simultaneously maintaining the highly crystalline architecture are still limited and highly desired. In this work, a facile construction methodology was demonstrated to afford g-C 3 N 4 with abundant N vacancies, high crystallinity, a hydrophilic surface structure, a small particle size, and an increased surface area under neat and mild conditions. Furthermore, the essence of our approach lies in the treatment of the bulk g-C 3 N 4 precursor with an alkaline salt (LiN(SiMe 3 ) 2 ) with a low melting point, moderate nucleophilicity, and easy removal procedures. The unique structural properties of the afforded ND-g-C 3 N 4 allow for a significantly redshifted absorption edge and enhanced charge carrier separation, leading to superior photocatalytic hydrogen evolution performance three times that obtained by pristine g-C 3 N 4 . The modification strategy developed herein sheds light on the fabrication of g-C 3 N 4 -based materials with improved photocatalytic efficiency via efficient introduction of N defects, variation of the surface structure, and retention of the high crystallinity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Cost-effective carbon fiber precursor selections of polyacrylonitrile-derived blend polymers: carbonization chemistry and structural characterizations

Blending polyacrylonitrile (PAN) with plastic wastes and bio-based polymers provides a convenient and inexpensive method to realize cost-effective carbon fiber (CF) precursors. In this work, PAN-based blend precursors are investigated using ReaxFF reactive molecular dynamics simulations with respect to the formation of all-carbon rings, the evolutions of oxygen-containing and nitrogen-containing species, and the migration of carbon atoms to form turbostratic graphene. From these simulations, we identify that PAN/cellulose (CL) blend manifests the highest carbon yield and the most substantial all-carbon ring formation. This ReaxFF-based finding is confirmed by Raman and TEM experiments indicating high crystallinity for PAN/CL-derived blend CFs. We trace the pathway of gasification and carbonization of PAN/CL to elaborate the mechanism of the formation of all-carbon ring networks. We discover that the acetals of CL can catalyze the cyclization of the blend precursor, allowing for the search for CL derivatives or the other kinds of bio-based polymers with similar functionalities as alternative blends. In addition, we examine the structural characteristics using the carbon–carbon (C–C) radial distribution functions, C–C bond length distributions, and sp2 C atom ratios for the four representative precursors, i.e., PAN, oxidized PAN, PAN/nylon 6,6, and PAN/CL. Our simulation results show the most extensive all-carbon ring cluster and graphitic structure growths for PAN/CL. Here, we propose PAN/CL as a cost-effective alternative CF precursor, since (a) CL is naturally abundant and eco-friendly for production, (b) the blend precursor PAN/CL does not require oxidation treatment, (c) PAN/CL has a high carbon yield with substantial all-carbon ring formation, and (d) PAN/CL based CFs potentially provide a mechanical property enhancement.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Electrochemically induced crystallization of amorphous materials in molten MgCl2: boron nitride and hard carbon

A novel and versatile strategy for the amorphous-to-crystalline transformation of boron nitride (BN) with the capability to control the degree of crystallization was developed through an electrochemical pathway using MgCl 2 at low temperature (750 °C). This procedure can be extended to the transformation of amorphous carbon to graphite, which significantly reduces the energy and cost, accelerates the synthesis process and could potentially replace industrial graphite synthesis globally. Therefore, the synthesized graphite exhibits much enhanced electrochemical performance at high charge–discharge rates (5C) compared to commercial synthetic graphite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Influence of pre-existing defects on thermal transport in nuclear graphite

Nuclear graphite is a critical material in high-temperature nuclear reactors due to its superior thermal and mechanical properties. The manufacturing process leaves multi-scale ‘pre-existing’ defects that can affect thermal transport characteristics. Because these defects are remnant of graphitization temperature, they cannot be thermally annealed. This study employs a non-thermal electron wind force (EWF) annealing technique to avoid this obstacle. 2 min of EWF treatment of the as-received graphite IG-110 at temperatures below 100 °C led up to 67% increase in thermal diffusivity and ~ 35% decrease in electrical resistivity in average. Differential scanning calorimetry also showed similar outcome for specific heat. X-ray diffraction characterization was performed by fitting a bi-modal crystallite size distribution model to reveal the enhancement in crystallinity after the EWF treatment. The findings emphasize the potential of EWF annealing for optimizing thermal performance in nuclear graphite and its implications for reactor efficiency and safety.

Annealing↗

DOE OSTI2022

Development of Nanocrystalline Graphite from Lignin Sources

Carbon composites are attractive to a variety of high-impact applications, such as carbon fibers, batteries, and vehicle parts, due to their multifunctional properties. The properties of carbon are highly dependent on the allotrope the carbon takes and the functionality, impurities, and defects contained within the structure. The increase in demand for sustainable carbon sources in energy storage devices motivates interest in understanding synthesis parameters of lignin value-added products. Also, as the dependence on oil for fuel decreases, alternative sources for carbon in many applications will be needed. In this work, the thermochemical conversion of lignin powders from different feedstocks was evaluated via small and wide-angle X-ray scattering techniques to resolve the amorphous, disordered, and crystalline domains present in the lignin carbons. Scattering analyses indicated an evolution of hierarchical structures along with an increase in ordered domains as a function of carbonization temperature. Qualitative and quantitative methods were used to describe isotropic scattering intensity profiles at multiple length scales. The use of power law models in the mesoscopic region served as the basis to describe morphological changes related to structural features, for example, graphene stacking, degree of roughness, and surface fractals. Kraft softwood and switchgrass produced carbon powder with the most crystalline domains and the least surface roughness. Softwoods reached the highest degree of crystallinity followed by switchgrass samples and had less variability in particle sizes. These results suggest lignin carbons extracted from softwoods and switchgrass are viable substitutes for graphite. Interpretation of X-ray scattering data from lignin carbon powders elucidates feedstock- and processing-dependent morphological features across multiple length scales providing a straightforward framework to evaluate the feasibility of leveraging lignin carbons for producing tunable application-specific materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Davis Computational Spectroscopy Workflow—From Structure to Spectra

Here, we describe an automated workflow that connects a series of atomic simulation tools to investigate the relationship between atomic structure, lattice dynamics, materials properties, and inelastic neutron scattering (INS) spectra. Starting from the atomic simulation environment (ASE) as an interface, we demonstrate the use of a selection of calculators, including density functional theory (DFT) and density functional tight binding (DFTB), to optimize the structures and calculate interatomic force constants. We present the use of our workflow to compute the phonon frequencies and eigenvectors, which are required to accurately simulate the INS spectra in crystalline solids like diamond and graphite as well as molecular solids like rubrene. We have also implemented a machine-learning force field based on Chebyshev polynomials called the Chebyshev interaction model for efficient simulation (ChIMES) to improve the accuracy of the DFTB simulations. We then explore the transferability of our DFTB/ChIMES models by comparing simulations derived from different training sets. We show that DFTB/ChIMES demonstrates ~100× reduction in computational expense while retaining most of the accuracy of DFT as well as yielding high accuracy for different materials outside of our training sets. The DFTB/ChIMES method within the workflow expands the possibilities to use simulations to accurately predict materials properties of increasingly complex structures that would be unfeasible with ab initio methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2009

Mineralogy of the Almahata Sitta Ureilite

Mineralogy & Petrography: Almahata Sitta, deriving from the asteroid 2008 TC3, is a coarse-grained- to porous, fine-grained, fragmental breccia with subrounded mineral fragments and olivine aggregates embedded in a cataclastic matrix of ureilitic material. Mineral fragments include polycrystalline olivine, low-calcium, pigeonite, and augite. Abundant carbonaceous aggregates containing graphite, microdiamonds and aliphatics. Kamacite, Cr-rich troilite, silica and schreibersite are abundant. The compositional range of the silicates is characteristic of the ureilites as a group, but unusually broad for an individual ureilite. The dense lithology is typical for ureilites, but the porous lithology is anomalous. In the porous lithology pore walls are largely coated by crystals of olivine. Classification: Almahata Sitta is an anomalous, polymict eucrite. Anomalous features include large compositional range of silicates, high abundance and large size of pores, crystalline pore wall linings, and fine-grained texture. Tomography reveals that the pores define thin, discontinuous "sheets" connected in three dimensions, suggesting that they outline grains that have been incompletely welded together. The crystals lining the pore walls are probably vapor phase deposits. Therefore Almahata Sitta may represent an agglomeration of coarse- to fine-grained, incompletely reduced pellets formed during impact, and subsequently welded together at high temperature.

Zolensky, Michael E.↗

DOE OSTI2022

High-efficiency, anode-free lithium–metal batteries with a close-packed homogeneous lithium morphology

Anode-free lithium–metal batteries (LMBs) are ideal candidates for high-capacity energy storage as they eliminate the need for a conventional graphite electrode or excess lithium–metal anode. Current anode-free LMBs suffer from low Coulombic efficiency (CE) due to poor lithium stripping efficiency. Advanced electrolyte development is a promising route to maximize lithium plating and stripping CE and minimize capacity fade. However, a poor understanding of the mechanisms by which advanced electrolytes improve performance hampers progress in the practical development of anode-free LMBs. Here, we use synchrotron techniques and other tools to analyze the influence of three commercially available electrolytes on the composition, heterogeneity, kinetics, morphology, and electrochemistry of anode-free LMBs. Advanced electrolytes improve the electrochemical performance of anode-free LMBs by forming much denser and better-packed Li morphologies on a Cu current collector than on the conventional electrolyte. Li plates uniformly over the electrode area with the advanced electrolytes rather than in a few active sites. Inactive crystalline Li with heterogeneous distribution dominates the capacity degradation of anode-free cells, especially with the conventional electrolyte, indicating that reducing the amount of “dead” crystalline Li will significantly improve the cycling stability of anode-free cells. Finally, the understanding of the Li plating and stripping process obtained from this work will accelerate the development of anode-free LMBs with high efficiency.

25 ENERGY STORAGE↗

DOE OSTI2024

Influence of gadolinium doping on structural, optical, and electronic properties of polymeric graphitic carbon nitride

Polymeric graphitic carbon nitride (gCN) materials have received great attention in the fields of photo and electrocatalysis due to their distinct properties in metal-free systems with high physicochemical stability. Nevertheless, the activity of undoped gCN is limited due to its relatively low specific surface area, low conductivity, and poor dispersibility. Doping Gd atoms in a gCN matrix is an efficient strategy to fine-tune its catalytic activity and its electronic structure. Herein, the influence of various wt% of gadolinium (Gd) doped in melon-type carbon nitride was systematically investigated. Gadolinium-doped graphitic carbon nitride (GdgCN) was synthesized by adding gadolinium nitrate to dicyandiamide during polymerization. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the crystallinity and the morphological properties are influenced by the % of Gd doping. Furthermore, X-ray photoelectron spectroscopy (XPS) studies revealed that the gadolinium ions bonded with nitrogen atoms. Complementary density functional theory (DFT) calculations illustrate possible bonding configurations of Gd ions both in bulk material and on ultrathin melon layers and provide evidence for the corresponding bandgap modifications induced by gadolinium doping.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Neutron thermalization in nuclear graphite: A modern story of a classic moderator

Graphite has been of great interest since the dawn of the nuclear era. In this work, we will focus on the thermal neutron scattering of two types of nuclear graphite that have different microstructures, namely, the historic PGA which has a very anisotropic medium-grained needle coke, and the new G347A which is a near-isotropic fine-grained graphite. We report the results of room temperature inelastic neutron scattering measurements for the scattering function, double differential scattering cross-section, and phonon density of states. The obtained results are discussed in conjunction with results extracted from first-principles lattice dynamics simulations of crystalline graphite, using the incoherent approximation and by also including the coherent-one phonon contribution. Excellent agreements have been found between the measured and calculated scattering functions and phonon densities of states. The inclusion of the coherent-one phonon scattering shows a significant improvement of the calculated scattering functions, double differentials, and inelastic scattering cross-sections. We also highlight the physical concerns about the current thermal neutron scattering ENDF/B-VIII of nuclear graphite library and its corresponding phonon density of states. This work aims to provide a new presentation of neutron thermalization by graphite and offers a new set of high quality experimental and computational data for consideration.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS2001

Flame Synthesis Used to Create Metal-Catalyzed Carbon Nanotubes

Metal-catalyzed carbon nanotubes are highly ordered carbon structures of nanoscale dimensions. They may be thought of as hollow cylinders whose walls are formed by single atomic layers of graphite. Such cylinders may be composed of many nested, concentric atomic layers of carbon or only a single layer, the latter forming a single-walled carbon nanotube. This article reports unique results using a flame for their synthesis. Only recently were carbon nanotubes discovered within an arc discharge and recognized as fullerene derivatives. Today metal-catalyzed carbon nanotubes are of great interest for many reasons. They can be used as supports for the metal catalysts like those found in catalytic converters. Open-ended nanotubes are highly desirable because they can be filled by other elements, metals or gases, for battery and fuel cell applications. Because of their highly crystalline structure, they are significantly stronger than the commercial carbon fibers that are currently available (10 times as strong as steel but possessing one-sixth of the weight). This property makes them highly desirable for strengthening polymer and ceramic composite materials. Current methods of synthesizing carbon nanotubes include thermal pyrolysis of organometallics, laser ablation of metal targets within hydrocarbon atmospheres at high temperatures, and arc discharges. Each of these methods is costly, and it is unclear if they can be scaled for the commercial synthesis of carbon nanotubes. In contrast, flame synthesis is an economical means of bulk synthesis of a variety of aerosol materials such as carbon black. Flame synthesis of carbon nanotubes could potentially realize an economy of scale that would enable their use in common structural materials such as car-body panels. The top figure is a transmission electron micrograph of a multiwalled carbon nanotube. The image shows a cross section of the atomic structure of the nanotube. The dark lines are individual atomic layer planes of carbon, seen here in cross section. They form a nested series of concentric cylinders, much like the growth rings on a tree. This sample was obtained by the supported catalyst method, whereby the nanoscale catalysts are dispersed on a substrate providing their support. The substrate with catalyst particles was immersed within an acetylene diffusion flame to which nitrogen had been added to eliminate soot formation. Upon removal from the flame, the nanotubes were dispersed on a holder suitable for electron microscopy. Although not seen in the figure, the tube diameter reflects that of the catalyst particle.

VanderWal, Randy L.↗

DOE OSTI2023

Low Cost Glass-Ceramic Matrix Composite Heat Exchanger

As part of ARPA-E’s High Intensity Thermal Exchange through Materials and Manufacturing Processes (HITEMMP) program, this project sought to develop novel heat exchanger (HX) capabilities to enable efficient and power dense power generation cycles. This class of HX comes under the category of ceramic/composite materials with the higher temperature goal in the program of ≥1100 °C inlet temperature operation. The enabling capability of this effort is the use of glass-ceramic matrix composite (GCMC) material which provides the high temperature durability of a ceramic, the flaw tolerance of a composite, a significantly faster and lower cost manufacturing process than conventional matrix CMCs and very low porosity levels < 0.5%. For thin-walled HX structures and the need to minimize leakage, the low porosity differentiator is particularly important. RTRC has prior experience with this material system and in the current project advanced the component design and manufacturing methods into new territory to produce features required for effective heat exchange under high pressures. In this approach, silicon carbide fiber is fabricated into a fiber preform using various textile processes. Graphite tooling is used both during the build-up of the fiber preform (interior tooling) and after the fiber preform has been completed (exterior tooling). This tooling assembly is heated to high temperature in an environment that has been evacuated and backfilled with inert gas. A reservoir of specialty glass is present and once the desired temperature has been reached to achieve the desired glass viscosity, an actuator distributes the glass throughout the fiber preform using passageways which are part of the tooling design in a process known as glass transfer molding. After the tooling has been removed, the composite is heat treated to convert the amorphous glass to a crystalline ceramic, providing improved properties. The project was divided into three phases focusing on the following: 1) 10 kW HX design and coupon-level tube sheet fabrication, 2) 10 kW HX fabrication, 3) 50 kW HX fabrication. During Budget Period 1 (BP1), additional risks were encountered and the need for additional funds was agreed upon by ARPA-E program leadership. Due to a variety of factors, the contract modification required nominally 18 months to execute at which time the HITEMMP program was effectively concluding. Because of this and the time that would be required to perform BP2 tasks, it was decided to conclude the project at the end of BP1. During the design of the 10 kW HX, manufacturing constraints were learned and incorporated, leading to a revised configuration for the fiber preform and HX. Heat exchange and pressure drop predictions also played a role in modifying the original design concept to be a higher aspect ratio shell-and-tube HX, simplifying the manufacturing process and improving the heat exchanger performance. Good gravimetric and volumetric thermal power densities of 11.2 kW/kg and 10,200 kW/m3 for the entire HX were projected that involved thermo-structural Finite Element Analysis to determine the structural mass needed for the high operation pressures of 250 bar cold inlet and 80 bar hot inlet. Fiber preforms using textile processes were produced for multiple headered tube sheets. Additional challenges were encountered during the glass transfer molding step for which solutions were identified, but programmatics did not allow them to be implemented in BP1. While complete HX test articles were not fabricated, the benefits of this GCMC material for a variety of high temperature applications remain.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2020

Visualizing Energy Transfer at Buried Interfaces in Layered Materials Using Picosecond X-Rays

Understanding the fundamentals of nanoscale heat propagation is crucial for next-generation electronics. For instance, weak van der Waals bonds of layered materials are known to limit their thermal boundary conductance (TBC), presenting a heat dissipation bottleneck. In this paper we present a new non-destructive method to probe heat transport in nanoscale crystalline materials using time-resolved x-ray measurements of photo-induced thermal strain. This technique directly monitors time-dependent temperature changes in the crystal and the subsequent relaxation across buried interfaces by measuring changes in the c-axis lattice spacing after optical excitation. We investigate films of five different layered transition metal dichalcogenides MoX 2 [X= S, Se, Te] and WX 2 [X= S, Se] as well as graphite and a W-doped alloy of MoTe 2 , on c-plane sapphire substrates, finding TBC values in the range 10-30 MWm -2 K -1 at room temperature. In conjunction with molecular dynamics simulations, we show that the high thermal resistances are a consequence of weak interfacial van der Waals bonding and low phonon irradiance. This work paves the way for an improved understanding of thermal bottlenecks in emerging three-dimensional heterogeneously integrated technologies.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Interpretation of wide-angle x-ray diffraction patterns from mesophase pitch-based carbon fibers – a simulation and experimental study

Carbon fiber is a critical material in a wide range of industries, where it is highly valued for its high specific strength/stiffness, excellent wear resistance, efficient electrical and thermal transport properties, chemical resistance, and low coefficient of thermal expansion. The properties of a specific carbon fiber are closely tied to its structural characteristics at all length scales. Here, in this work, we applied wide-angle x-ray diffraction to a set of heat-treated mesophase pitch-based carbon fibers, with the goal of elucidating the crystalline structures as a function of fiber orientation. To assist with analysis and interpretation of the experimental data, we employed diffraction pattern simulations using the scalar and vector forms of the Debye scattering equation to determine the influence of basal plane orientation, crystalline ordering (turbostratic-graphitic), and basal plane asymmetry on the diffraction patterns. The results presented here suggest that growth of the transverse crystallites in mesophase pitch-based carbon fiber is fixed until graphitization temperatures are reached. The work completed here provides a framework for the analysis of carbon fiber and other oriented carbon-based materials via diffraction.

36 MATERIALS SCIENCE↗

NASA NTRS1994

The nature of carbon-bearing phases in hydrated interplanetary dust particles

We have been quantitatively measuring C abundances in hydrated interplanetary dust particles for the past few years, but in general, we have had to infer the distribution and nature of the C-bearing materials within these particles because of the complex microtextures of hydrated IDPs. Aside from rare carbonate grains, other C-bearing phases are difficult to distinguish from the fine-grained, poorly crystalline phyllosilicates that comprise the bulk of these particles. We know that carbonates alone cannot account for the high C abundances observed in most hydrated IDPs and that additional C-bearing phases must be present. We have recently applied the technique of electron energy-loss spectroscopy (EELS) in the transmission electron microscope (TEM) to identify and form the distribution of C-bearing phases in hydrated IDPs. These preliminary data show that several C-rich hydrated IDPs contain a mixture of two major forms of C, Mg-Fe carbonate and amorphous C. The near-edge structure in the C k-edges from these IDPs shows no evidence for the development of graphite or even poorly graphitized C. We conclude that the 'elemental' C in these IDPs is either very poorly ordered or is exceedingly fine-grained (we refer to this C as 'amorphous C'). The amorphous C is intimately intergrown with the fine-grained phyllosilicates and is evenly distributed within three of the four IDPs analyzed (only G1 contains discrete 'hot spots' of amorphous C). Not all hydrated IDPs contain carbonates.

Keller, L. P.↗

DOE OSTI2022

Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts

To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm 1.5 Sr 0.5 NiO 4 Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm 2 O 3 composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm 2 O 3 or Ni/Sm 2 O 3 /SrCO 3 materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm 1.5 Sr 0.5 NiO 4 , and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO 3 in the case of Sm 1.5 Sr 0.5 NiO 4 , which is dominant at high temperatures. For Sm 1.5 Sr 0.5 NiO 4 , the CO : H 2 ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO 3 without catalytic DRM reactivity. As no Sm 2 O 2 CO 3 surface or bulk phase as a result of carbon dioxide activation was observed for any material – in contrast to La 2 O 2 CO 3 – we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm 1.5 Sr 0.5 NiO 4 and NiO/monoclinic Sm 2 O 3 after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm 2 O 3 facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm 2 O 3 interface by favoring Ni particle sintering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2003

Review of Laser Ablation Process for Single Wall Carbon Nanotube Production

Different types of lasers are now routinely used to prepare single wall carbon nanotubes (SWCNTs). The original method developed by researchers at Rice University utilized a "double pulse laser oven" process. A graphite target containing about 1 atomic percent of metal catalysts is ablated inside a 1473K oven using laser pulses (10 ns pulse width) in slow flowing argon. Two YAG lasers with a green pulse (532 nm) followed by an IR pulse (1064 nm) with a 50 ns delay are used for ablation. This set up produced single wall carbon nanotube material with about 70% purity having a diameter distribution peaked around 1.4 nm. The impurities consist of fullerenes, metal catalyst clusters (10 to 100 nm diameter) and amorphous carbon. The rate of production with the initial set up was about 60 mg per hour with 10Hz laser systems. Several researchers have used variations of the lasers to improve the rate, consistency and study effects of different process parameters on the quality and quantity of SWCNTs. These variations include one to three YAG laser systems (Green, Green and IR), different pulse widths (nano to microseconds as well as continuous) and different laser wavelengths (Alexandrite, CO, CO2, free electron lasers in the near to far infrared). It is noted that yield from the single laser (Green or IR) systems is only a fraction of the two laser systems. The yield seemed to scale up with the repetition rate of the laser systems (10 to 60 Hz) and depended on the beam uniformity and quality of the laser pulses. The shift to longer wavelength lasers (free electron, CO and CO2) did not improve the quality, but increased the rate of production because these lasers are either continuous (CW) or high repetition rate pulses (kHz to MHz). The average power and the peak power of the lasers seem to influence the yields. Very high peak powers (MegaWatts per square centimeter) are noted to increase ablation of bigger particles with reduced yields of SWCNTs. Increased average powers seem to help the conversion of the carbon from target into vapor phase to improve formation of nanotubes. The use of CW far infrared lasers reduced the need for the oven, at the expense of controlled ablation. Some of these variations are tried with different combinations and concentrations of metal catalysts (Nickel with Cobalt, Iron, Palladium and Platinum) different buffer gases (e.g. Helium); with different oven temperatures (Room temperature to 1473K); under different flow conditions (1 to 1000 kPa) and even different porosities of the graphite targets. It is to be noted that the original Cobalt and Nickel combination worked best, possibly because of improved carbonization with stable crystalline phases. The mean diameter and yield seemed to increase with increasing oven temperatures. Thermal conductivity of the buffer gas and flow conditions dictate the quality as well as quantity of the SWCNTs. Faster flows, lower pressures and heavier gases seem to increase the yields. This review will attempt to cover all these variations and their relative merits. Possible growth mechanisms under these different conditions will also be discussed.

Arepalli, Sivaram↗