Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “additive”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Effect of Li metal addition on corrosion control of Hastelloy N and stainless steel 316H in molten LiF-NaF-KF

Molten fluoride salts are used in various energy harvesting applications such as solar collectors and molten salt nuclear reactors (MSRs). Thermodynamically driven selective dissolution of alloying elements due to impurities present within the fluoride salts have been identified to be the main corrosion mechanism for structural alloys in molten fluoride salts. Impurities in these salts, during salt preparation as well as during operation, can be difficult to control. One way to prevent the selective dissolution of active alloying elements is to make the molten salt reducing by either purifying it to remove impurities or to add some reactive metal that will react with the impurities and make the salt reducing. Here this study is focused on the corrosion behaviour of Hastelloy N and 316H stainless steel in molten LiF-NaF-KF eutectic mixture (FLiNaK) at 700°C and how this behaviour changes with the addition of Li metal as a reducing impurity. Our results indicate that the active metal addition like Li can be very effective in controlling the redox behaviour of salt, which in-turn can mitigate corrosion. Even the addition of small quantities of Li metal can mitigate the selective dissolution of active alloying elements for the tested structural materials in FLiNaK. Our results also suggest that the presence of excess amounts of Li, above the minimum concentration required to react with the impurities in FLiNaK, does not have any detrimental effect in terms of formation of new intermetallic phases at the surface of the selected alloys under tested conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Polysulfide-incompatible additive suppresses spatial reaction heterogeneity of Li-S batteries

Rational electrolyte engineering for practical pouch cells remains elusive because the correlation between the cathode/solid-electrolyte interphase layer and cell-level reaction behavior is poorly understood. Here, by combining multiscale characterization and computational modeling, we show that—counter to the conventional perception of polysulfide-incompatible additives—the spontaneous reaction of sparingly solvated polysulfides with Lewis acid additives (LAAs) can induce in situ formation of a homogeneous interphase on thick and tortuous S cathode. Multiscale synchrotron X-ray characterization consistently affirms that such interface design could effectively eliminate the notorious problems of polysulfide shuttle and lithium corrosion and, more importantly, provide an interconnected “ion transport highway” to alleviate the uneven ion transport within the tortuous S cathode. Hence, this design dramatically reduces the reaction heterogeneity of lithium-sulfur (Li-S) pouch cells under lean electrolyte conditions. Further, this work resolves controversy around the role of polysulfide-incompatible additives in high-energy Li-S pouch cells and highlights the importance of suppressing reaction heterogeneity for practical batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Additives and solvents-induced phase and morphology modification of NaYF{sub 4} for improving up-conversion emission

Both cubic and hexagonal NaYF{sub 4} were synthesized in different reaction systems via hydro/solvo-thermal route. The effects of reaction temperature, solvents, and additives on the synthesis of NaYF{sub 4} have been studied in detail. It has been shown that phase transformation from cubic NaYF{sub 4} to hexagonal NaYF{sub 4} always occurred. The sequence of the ability for inducing the phase transformation was ethanol>H{sub 2}O>acetic acid. It is found that ethanol can not only facilitate the formation of hexagonal NaYF{sub 4} but also control the growth of the crystal. This is quite unusual for the growth of H-NaYF{sub 4}. The up-conversion emission properties of Yb/Er co-doped NaYF{sub 4} have also been investigated and the results demonstrated some general principles for improving up-conversion emission. - Graphical abstract: Additives and solvents can induce the phase transformation of NaYF{sub 4}, typically the use of organic sodium salt and ethanol. - Highlights: • The effect of additives and solvents on the synthesis of NaYF{sub 4} was studied in detail. • Ethanol can facilitate the formation of H-NaYF{sub 4} while acetic acid restrain it. • Three general principles for improving up-conversion emission were summarized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The effect of Sn addition on phase stability and phase evolution during aging heat treatment in Ti–Mo alloys employed as biomaterials

Increases in life expectancy and improvements in necessary healthcare attach great importance to the development of biomaterials. Ti alloys containing β stabilizing elements are often used as biomaterials due to their high specific strength, high corrosion resistance, unusual biocompatibility and low elastic moduli, which benefit bone tissues close to an implant. This study deals with phase stability in β Ti–Mo–Sn alloys processed under different conditions and was performed according to the following steps: a study of the effect of Sn content (a) on phase stability in Ti–Mo alloys, (b) on the suppression of α″ and ω phase precipitation; (c) on α-phase precipitation during aging heat treatments and (d) on mechanical properties, including the elastic modulus, as measured using tensile tests and acoustic techniques. The alloys were prepared by arc melting under a controlled atmosphere followed by homogenization heat treatment and hot rolling. Optical microscopy, scanning and transmission electron microscopy, X-ray diffraction and differential scanning calorimetry were employed for characterization purposes. Samples were also submitted to solution treatment above the β transus temperature and aging heat treatments under a controlled atmosphere. The results suggest that Sn suppresses the formation of the ω and α″ phases in Ti–Mo system. - Highlights: • Sn addition to Ti alloys decreases elastic modulus by suppressing ω phase precipitation. • Sn addition decreases the temperature of martensite decomposition. • Sn addition decreases the temperature of α phase precipitation and β transus. • Mechanical strength decreases with increasing Sn content.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Characterization of ZnAl cast alloys with Na addition

This study was aimed at evaluating the microstructural change and thermal, electrical and mechanical properties with the addition of Na to eutectic ZnAl alloys. Solders based on eutectic ZnAl containing 0.2 to 3.0 (wt.%) of Na were developed for high temperature solder. Differential scanning calorimetry (DSC) measurements were performed to determine the melting temperatures of the alloys. Thermal linear expansion and electrical resistivity measurements were performed over − 50 °C to 300 °C and 30 °C to 300 °C temperature ranges, respectively. The microstructure of the specimens was analyzed using scanning (SEM) and transmission electron microscopy (TEM) techniques. Chemical microanalysis was performed by energy-dispersive X-ray spectroscopy (EDS) on SEM and TEM. The precipitates of NaZn{sub 13} were confirmed by X-ray diffraction (XRD) measurements and selected area electron diffraction (SAED) techniques. The addition of Na to eutectic ZnAl alloy increased the electrical resistivity and reduced the coefficient of thermal expansion; however, the melting point did not change. The mechanical properties, strain and microhardness increased with Na content in alloys. - Highlights: • High temperature soldering materials of ZnAl with Na were designed and characterized. • Precipitates of NaZn{sub 13}were observed and confirmed using TEM and XRD. • Addition of Na to eutectic ZnAl cussed increased mechanical properties. • NaZn{sub 13} caused increased electrical resistivity and microhardness, and reduced the CTE.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Effect of bioglass 45S5 addition on properties, microstructure and cellular response of tetracalcium phosphate/monetite cements

Tetracalcium phosphate/nanomonetite (TTCPMH) cement composites with 7.5 and 15 wt% addition of melt-derived 45S5 bioactive glass were prepared by mechanical homogenization of powder components and 2% NaH{sub 2}PO{sub 4} solution was used as a hardening liquid. The properties of composites with the acidic (Ca/P ratio equal 1.5) or basic (Ca/P ratio equal 1.67) TTCPMH component were compared. Addition of glass component caused rapid rise in pH of composites up to 10. In microstructure of basic cement composite, the large bioglass particles weakly bounded to surrounding cement matrix were found contrary to a more compact microstructure of acidic cement composites with the high number of spherical silica particles. Both the significant refinement of hydroxyapatite particles and the change to needle-like morphology with rise in the content of bioglass were identified in hydroxyapatite coatings created during soaking of composites in phosphate buffered saline. In acidic cement mixtures, the increase of compressive strength with an amount of bioglass was found whereas the opposite tendency was revealed in the case of basic cement mixtures. The higher concentrations of ions were verified in solutions after immersion of acidic cement composites. The severe cytotoxicity of extracts and composite cement substrates containing 15 wt% of bioglass demonstrated adverse effects of both the ionic concentrations and unappropriate surface texture on proliferation of mesenchymal stem cells. The enhanced ALP activities of cells cultured on composite cements confirmed the positive effect of bioactive glass addition on differentiation of mesenchymal stem cells. - Highlights: • Novel B45S5 bioglass/tetracalcium phosphate/nanomonetite cement composites • Cement basicity negatively affected their microstructure. • Acid composite cements had higher compressive strengths than basic composites. • Fast differentiation of MSC to osteoblast line on composite with 7.5 wt% of bioglass • Severe cytotoxicity of 24 h extracts from composites with 15 wt% of bioglass.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The effects of Cr particles addition on the aging behavior and mechanical properties of SiCp/7075Al composites

Highlights: • The novel investigated the effects of Cr particles on the aging behavior and mechanical properties of SiC{sub p}/7075Al composites. • The addition of Cr particles didn't change precipitation sequence, but significantly degraded precipitation kinetics of composites. • Cr particles had a significant effect on the tensile properties of the peak-aged composite because of Mg aggregation. - Abstract: The effects of Cr particles addition on the aging behavior and mechanical properties of SiC{sub p}/7075Al composites were systematically investigated. The results show that the precipitation sequence of (5 vol% Cr + 50 vol% SiC)/7075Al composites (C-7075Al) is still: GP zone → η′ → η (MgZn{sub 2}), but Cr particles degrade the precipitation kinetics of the C-7075Al composite in comparison to (5 vol% SiC{sub p} + 50 vol% SiC{sub p})/7075Al (B-7075Al) because of reduced dislocation density present in the matrix and higher thermal activation energy of the η′ phase. Besides, the addition of Cr particles has a significant effect on the mechanical properties of the C-7075Al composite during the aging process. In contrast to the as-cast state, the ultimate tensile strength of the C-7075Al composite obtains an increase of 120 MPa at the peak-aged period, significantly lower than those of 7075Al alloy (207 MPa) and the B-7075Al composite (151 MPa), which is attributable to the severe aggregation of elemental Mg at the interface between Cr particles and the Al matrix.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Influence of Mn addition on the microstructure and mechanical properties of a directionally solidified γ-TiAl alloy

Highlights: • Mn addition can significantly improve the yield strength of TiAl alloy. • Introduction of Mn facilitates the operation of twinning-controlled deformation. • Twin-dislocation interactions cause a continuous increase in work hardening rate. - Abstract: TiAl alloys with nominal compositions of Ti-47Al-2Nb-2Cr-(0, 1, 3, 5)Mn were prepared via electromagnetic cold crucible directional solidification (ECCDS), and the influence of Mn addition on the microstructure and mechanical properties of the alloys was investigated. The experimental results showed that the Mn atoms were dissolved within the TiAl alloy, and no Mn compounds were formed. Based on the X-ray diffraction (XRD) analysis results, the peak angle of the Mn-containing sample shifted to a higher value, indicating lattice shrinkage. The Mn addition also increased the volume fraction of the B2 phase. The yield strength of the TiAl alloy monotonically increased as the content of the substitutional-solute Mn atoms increased. The ultimate strengths of the TiAl alloys containing 1 at.%, 3 at.%, and 5 at.% Mn consequently decreased because micro-cracks were preferentially formed in the B2 phase during room-temperature deformation. The introduction of substitutional-solute Mn atoms could result in a reduction of the stacking-fault energy of the γ phase, and facilitate the operation of twinning-controlled plastic-deformation during the intermediate stage of the plastic deformation process. The interaction between the deformation twins and movable dislocations led to a continuous increase in the work-hardening rate.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modification of microstructure and properties of Ti-47Al-2Cr-4Nb-0.3W alloys fabricated by SPS with trace multilayer graphene addition

Highlights: • The TiAl alloys with different content addition of multilayer graphene were fabricated. • When the graphene content is 0.8 at.%, the mean grain size decreases to 8.2 μm. • The bending and fracture strength increase to 1000 MPa and 2347 MPa, respectively. • The friction coefficient decreased from 0.6 to 0.4, with a decrease by 1/3. - Abstract: In this paper, Ti-47Al-2Cr-4Nb-0.3W alloys with trace multilayer graphene addition were fabricated by spark plasma sintering to enhance both mechanical properties and tribological property simultaneously. With the addition of multilayer graphene, bending strength, compressive strength and tribological property of TiAl alloys are all improved. When graphene content increases from zero to 0.8 at.%, the mean grain size decreases from 14.8 ± 1.4 μm to 8.2 ± 0.8 μm. The bending strength reaches almost 1000 MPa and the fracture strength increases to 2347 ± 12 MPa, an increase of 15% compared with TiAl alloy. The friction coefficient also decreases from about 0.6 to 0.4, a decrease by 1/3 compared with TiAl alloy. The reasons for the improved mechanical properties and tribological property are the in-situ reaction plate-shape Ti{sub 2}AlC phase, fine needle-like Ti{sub 3}AlC phase as well as fine and homogeneous microstructure. The wear mechanism changes from abrasive wear to abrasive wear plus adhesive wear with the increased graphene content.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Hydrogen embrittlement and mechanical response of 304L steel with ZrC additions

While stainless steels are widely used for hydrogen storage infrastructure, they can still be vulnerable to hydrogen embrittlement justifying the need to further improve their hydrogen resiliency. Here, we investigate the potential for transition metal carbide additions to improve the hydrogen compatibility of austenitic stainless steels. ZrC nanoparticles were dispersed in contents of 0.01–10 wt% in 304 L stainless steel powder, mixed via high energy ball milling, and subsequently consolidated using direct current sintering. To assess hydrogen compatibility, the tensile properties of similarly processed 304 L without ZrC nanoparticles were compared to 304 L with the ZrC additions; both materials were evaluated prior to and after hydrogen exposure (non-charged and H-precharged, respectively). Depending upon the ZrC phase fraction, the yield strengths varied from ∼325 to 560 MPa in the non-charged condition and from ∼375 to 550 MPa in the H-precharged condition. Strain at failure varied from ∼5 to 90 % and from ∼5 to 35 % in the non-charged and hydrogen-precharged conditions, respectively. Results from stress-strain profiles demonstrate limited efficacy of ZrC as a method to mitigate hydrogen embrittlement entirely but does demonstrate the potency of ZrC inclusions as strengthening addition to 304 L alloys without a loss of ductility.

08 HYDROGEN↗
DOE OSTI2019

An extremely durable redox shuttle additive for overcharge protection of lithium-ion batteries

Redox shuttle additives are used to protect lithium ion batteries from electrolyte oxidation and overheating during overcharge conditions. The additive protects the cell by becoming involved in a futile redox cycle that pins the cathode potential near the redox potential of the shuttle molecule. Since the material eventually becomes consumed in side reactions, high solubility of the parent molecule and high chemical stability of the charged molecule are required for durable protective action. Furthermore, we demonstrate a highly soluble (0.6 M) 1,4-dialkoxybenzene redox shuttle molecule that provides overcharge protection over 500 cycles at a C/2 rate and 100% overcharge ratio, which places this additive far ahead of the current state of the art.

1,4-Dialkoxybenzene↗
DOE OSTI2022

Strengthening of nanocrystalline Al using grain boundary solute additions: Effects of thermal annealing and ion irradiation

Strengthening of nanocrystalline Al by grain boundary solute additions was investigated for a series of dilute aluminum alloys, Al-Sc, Al-Sb, Al-Cr, and Al-W with grain sizes in the range of 50–200 nm. Thermal annealing of the alloys at low temperatures led to alloy softening, but with negligible change in the grain size. The re- duction in strength can be attributed to the loss of solute in the grain boundaries arising from grain boundary diffusion and precipitation. Annealing at higher temperatures led to grain growth, but with little additional loss of strength, a result of precipitation hardening. The Al-Sc and Al-Sb alloys were additionally subjected to ion irradiation at various temperatures. Furthermore, these studies revealed that annealed samples regained their hardness due to solute redistribution by ion beam mixing. Alloy strength was independent of grain size between 50 and 150 nms. Irradiation-induced segregation of Sb to grain boundaries in Al-Sb further enhanced strengthening.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dynamics of organic matter molecular composition under aerobic decomposition and their response to the nitrogen addition in grassland soils

Grassland soils store a substantial proportion of the global soil carbon (C) stock. The transformation of C in grassland soils with respect to chemical composition and persistence strongly regulate the predicted terrestrial-atmosphere C flux in global C biogeochemical cycling models. In addition, increasing atmospheric nitrogen (N) deposition alters C chemistry in grassland soils. However, there remains controversy about the importance of mineralogical versus biochemical preservation of soil C, as well as uncertainty regarding how grassland soil C chemistry responds to elevated N. This study used grassland soils with diverse soil organic matter (SOM) chemistries in an 8-month aerobic incubation experiment to evaluate whether the chemical composition of SOM converged across sites over time, and how SOM persistence responded to the N addition. This study demonstrates that over the course of incubation, the richness of labile compounds decreased in soils with less ferrihydrite content, whereas labile compounds were more persistent in ferrihydrite rich soils. In contrast, we found that the richness of more complex compounds increased over the incubation in most sites, independent of soil mineralogy. Moreover, we demonstrate the extent to which the diverse chemical composition of SOM converged among sites in response to microbial decomposition. N fertilization decreased soil respiration and inhibited the convergence of molecular composition across ecosystems by altering N demand for microbial metabolism and chemical interactions between minerals and organic molecules. This study provides original evidence that the decomposition and metabolism of labile organic molecules were largely regulated by soil mineralogy (physicochemical preservation), while the metabolism of more complex organic molecules was controlled by substrate complexity (biochemical preservation) independent to mineral-organic interactions. This study advanced our understanding of the dynamic biogeochemical cycling of C by unveiling that N addition dampened C respiration and diminished the convergence of SOM chemistry across diverse grassland ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Iron addition to soil specifically stabilized lignin

The importance of lignin as a recalcitrant constituent of soil organic matter (SOM) remains contested. Associations with iron (Fe) oxides have been proposed to specifically protect lignin from decomposition, but impacts of Fe-lignin interactions on mineralization rates remain unclear. Oxygen (O 2 ) fluctuations characteristic of humid tropical soils drive reductive Fe dissolution and precipitation, facilitating multiple types of Fe-lignin interactions that could variably decompose or protect lignin. Here, we tested impacts of Fe addition on 13 C methoxyl-labeled lignin mineralization in soils that were exposed to static or fluctuating O 2 . Iron addition suppressed lignin mineralization to 21% of controls, regardless of O 2 availability. However, Fe addition had no effect on soil CO 2 production, implying that Fe oxides specifically protected lignin methoxyls but not bulk SOM. Iron oxide-lignin interactions represent a specific mechanism for lignin stabilization, linking SOM biochemical composition to turnover via geochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nitrogen addition alters the relative importance of roots and mycorrhizal hyphae in regulating soil organic carbon accumulation in a karst forest

Plant belowground carbon (C) inputs from roots and associated mycorrhizal hyphae are increasingly recognized as critical drivers impacting soil organic C (SOC) pool. However, whether roots and mycorrhizal hyphae differentially regulate SOC formation and accumulation under elevated nitrogen (N) deposition remains to be addressed. Using an ingrowth-core technique, the relative contributions of roots and mycorrhizal hyphae to SOC accumulation were distinguished and quantified in a karst forest receiving three levels of N additions (control (0 kg N ha -1 yr -1 ), low N (150 kg N ha -1 yr -1 ) and high N (300 kg N ha -1 yr -1 )). Here our results showed that N addition stimulated SOC accumulation (indicated by the increase of both bulk SOC and mineral associated organic C fraction) influenced by both roots and hyphae, especially for higher N doses. Moreover, N addition increased the contribution of the root effect relative to the hyphal effect in the SOC accrual. The correlation analysis showed that, for the hyphal effect, the change in SOC content was solely and positively correlated with the change in protective mineral phases of SOC, but not with the microbial necromass. In contrast, for the root effect, the change in SOC content was significantly and positively correlated with the changes in both soil microbial C pump efficacy and protective mineral phases of SOC. These results suggest that roots and mycorrhizal hyphae may influence the accumulation of microbial necromass and the formation of mineral-organic associations in a different magnitude under enhanced N supply. These findings advance our understanding of the root-mycorrhizal interactions in mediating SOC dynamics in forests under future N deposition scenarios.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Effect of the addition of Si into V 2 O 5 coatings: Structure and tribo-mechanical properties

Vanadium oxide (V2O5) is one of the lubricious oxides with the potential to be used as a solid lubricant at elevated temperatures. However, the material itself is not hard wear-resistant, so most of the research has focused on adding V into hard nitride coatings that could lead to the formation of a self-lubricating V(2)O(5)layer when heated. The other possible solution, which has been less studied, is to look for mechanisms to enhance the hardness of the oxide coating. In this research, we investigate the effect of the addition of Si into the V2O5 coatings, aiming to find conditions that lead to enhance hardness and/or reduced wear while keeping the high temperature lubricity of the V2O5 structure. For this, Si modified V2O5 coatings were deposited using a dual magnetron sputtering system. The results showed that small additions of Si (< 2.0 at%) improved the hardness of the V2O5 coatings up to 5 times while keeping the same temperature dependence of the coefficient of friction than V2O5. Dry sliding experiments using the pin-on-disc configuration against silicon nitride balls were performed at 25, 300 and 600 degrees C. Wear factors in the 10(-7) mm(3)/Nm range were obtained, indicating a good wear resistance. Further addition of Si into the V2O5 structure led to a loss of the crystalline ordering and a significant reduction in the hardness.

Hall-Petch↗
DOE OSTI2022

Flow in additively manufactured super-rough channels

Metal additive manufacturing has enabled geometrically complex internal cooling channels for turbine and heat exchanger applications, but the process gives rise to large-scale roughness whose size is comparable to the channel height (which is 500 $\mathrm {\mu }$ m). These super-rough channels pose previously unseen challenges for experimental measurements, data interpretation and roughness modelling. First, it is not clear if measurements at a particular streamwise and spanwise location still provide accurate representation of the mean (time- and plane-averaged) flow. Second, we do not know if the logarithmic layer survives. Third, it is unknown how well previously developed rough-wall models work for these large-scale roughnesses. To answer the above practical questions, we conduct direct numerical simulations of flow in additively manufactured super-rough channels. Three rough surfaces are considered, all of which are obtained from computed tomography scans of additively manufactured surfaces. The roughness’ trough to peak sizes are 0.1 $h$ , 0.3 $h$ and 0.8 $h$ , respectively, where $h$ is the intended half-channel height. Each rough surface is placed opposite a smooth wall and the other two rough surfaces, leading to six rough-wall channel configurations. Two Reynolds numbers are considered, namely $Re_\tau =180$ and $Re_\tau =395$ . We show first that measurements at one streamwise and spanwise location are insufficient due to strong mean flow inhomogeneity across the entire channel, second that the logarithmic law of the wall survives despite the mean flow inhomogeneity and third that the established roughness sheltering model remains accurate.

Altland, Samuel↗
DOE OSTI2021

Transformation of an Embedded Five-Membered Ring in Polycyclic Aromatic Hydrocarbons via the Hydrogen-Abstraction–Acetylene-Addition Mechanism: A Theoretical Study

Five-membered rings are constituents of many polycyclic aromatic hydrocarbons (PAHs) and their presence on the edges of large PAHs has been repeatedly observed experimentally. However, modern kinetic combustion models often do not consider the growth of PAHs through the transformation of the five-membered rings. Here, in connection with the above, we carried out a theoretical study of the mechanism of Hydrogen-Abstraction-aCetylene-Addition (HACA) transformation of an embedded five-membered ring on the armchair PAH edge to a six-membered ring, considering cyclopenta[d,e,f]phenanthrene (4,5-methylenephenanthrene) as a prototype system for this process. The potential energy surface for the reactions of cyclopenta[d,e,f]phenanthrenyl radicals produced by direct H abstractions from cyclopenta[d,e,f]phenanthrene with acetylene has been compiled at the G3(MP2,CC)//B3LYP/6-311G(d,p) level of theory including zero-point vibrational energy corrections. The computed energies and molecular parameters were then used to solve the Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) in order to calculate reaction rate at various pressures and temperatures, which were fitted to modified Arrhenius equation for further kinetic modeling. The results show that the HACA transformation of the embedded five-membered ring to a six-membered ring is possible, albeit slow. The most viable reaction mechanism involves the R2 + C 2 H 2 reaction, where the acetylene molecules adds to a σ-radical in the six-membered ring adjacent to the five-membered ring via a low entrance barrier. The predominant product of R2 + C 2 H 2 is predicted to be 3 ethynyl 4H cyclopenta[def]phenanthrene Pr5 via immediate H elimination from the initial addition complex. Next, Pr5 undergoes H-assisted isomerization to 4aH-pentaleno[4,3,2,1-cdef]phenanthrene Pr4, and the latter adds an H atom eventually forming the 1-pyrenylmethyl radical Pr3: R2 + C 2 H 2 ⇌ 3 ethynyl 4H cyclopenta[def]phenanthrene (Pr5) + H ⇌ 4aH-pentaleno[4,3,2,1-cdef]phenanthrene (Pr4) + H Pr5 + H ⇌ Pr4 + H Pr4 + H → 1-pyrenylmethyl (Pr3) This HACA sequence may be competitive with the methyl radical addition to the R1 radical formed by H abstraction from the CH 2 group in the five-membered ring of cyclopenta[d,e,f]phenanthrene, which provides a pathway to pyrene following two H atom losses. Relative contributions of the two mechanisms of the five- to six-membered ring transformation would strongly depend on the branching ratios of the R1 and R2 radicals produced by the H abstractions and the available concentration of C 2 H 2 vs. CH 3 and hence differ in different flames.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗