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At least 19 records

Electrochemical C–N Bond Formation within Boron Imidazolate Cages Featuring Single Copper Sites

Electrocatalysis expands the ability to generate industrially relevant chemicals locally and on-demand with intermittent renewable energy, thereby improving grid resiliency and reducing supply logistics. Herein, we report the feasibility of using molecular copper boron-imidazolate cages, BIF-29(Cu), to enable coupling between the electroreduction reaction of CO 2 (CO 2 RR) with NO 3 – reduction (NO 3 RR) to produce urea with high selectivity of 68.5% and activity of 424 μA cm –2 . Remarkably, BIF-29(Cu) is among the most selective systems for this multistep C–N coupling to-date, despite possessing isolated single-metal sites. The mechanism for C–N bond formation was probed with a combination of electrochemical analysis, in situ spectroscopy, and atomic-scale simulations. We found that NO 3 RR and CO 2 RR occur in tandem at separate copper sites with the most favorable C–N coupling pathway following the condensation between *CO and NH 2 OH to produce urea. In conclusion, this work highlights the utility of supramolecular metal–organic cages with atomically discrete active sites to enable highly efficient coupling reactions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Prospects for Forming C–N Bonds from Dinitrogen

The formation of C–N bonds from molecular dinitrogen (N 2 ) offers a synthetic route to value-added nitrogen-containing compounds without relying on prefunctionalized nitrogen sources. Here, this Perspective highlights recent advances in forming C–N bonds from N 2 with homogeneous transition metal complexes. After discussing how transition metal complexes activate N 2 through various coordination modes, we focus on the reactivity of reduced nitrogen intermediates with different kinds of carbon sources. Carbon electrophiles and nucleophiles enable C–N bond formation via insertion, substitution, or radical pathways. Cycloaddition reactions, particularly involving polarized N 2 ligands and unsaturated carbon electrophiles, offer routes to more complex products. We describe efforts to achieve catalytic turnover and emphasize the remaining obstacles to catalytic C–N bond construction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Triggering C-N Coupling on Metal Oxide Nanocomposite for the Electrochemical Reduction of CO 2 and NO x ⁻ to Formamide

The co-electroreduction of CO 2 and NO x ⁻ (NO 3 ⁻ /NO 2 ⁻ ) to generate formamide (HCONH 2 ) offers an opportunity for downstream chemical and polymer manufacturing decarbonization; however, significant challenges lie in the C-N coupling and the associated low product selectivity. Herein, p-block metal oxides are incorporated in copper oxides to provide more accessible active sites for reactant adsorption and activation, tuning the reaction selectivity toward the formamide production. Through in situ Raman and synchrotron-based infrared spectroscopy measurements, C-N bond formation is demonstrated in real-time with the CuO x /BiO x catalyst, where the C-N bond is detected via a *CHO and *NH 2 intermediates formation, in agreement with the density functional theory calculations. When tested in a flow electrolyzer, a formamide yield rate of 134 ± 11 mmol h -1 g cat -1 is reported, the first report of co-electroreduction of CO 2 and NO x ⁻ to formamide beyond conventional H-cell measurements. These new insights on the C-N coupling mechanisms and scale-up capability provide directions for further development of electrocatalysts for the formamide production.

36 MATERIALS SCIENCE↗

Promoting the oxidative coupling of methanol and dimethylamine using group 1 alkali metals on palladium-gold nanoparticles

PdAu/SiO 2 catalysts were synthesized by strong electrostatic adsorption (SEA) and characterized by TEM, DRIFTS, XRD, XAS, and O 2 -TPD. The use of group 1 alkali salt solutions to control pH during SEA syntheses led to uptake of alkali metals observed reductions in the densities of terminal silanol groups of the SiO 2 support. In the absence of alkali metals, PdAu/SiO 2 catalyzes oxidative C-N bond formation between methanol and dimethylamine (DMA), yielding dimethylformamide (DMF) with ∼95 % carbon selectivity (CO 2 ∼5 %) at temperatures below 413 K. When Na, K, and Cs were present on the catalyst, methyl formate (MF) and tetramethylurea (TMU) were observed as additional products (combined ∼30 % carbon selectivity) while only TMU was detected for the Li-promoted catalyst. Total coupling product rate increased for promoted samples in the order Li < Na < Cs < K, and the apparent kinetics over the Cs-promoted catalyst were distinct from those over the alkali-free catalyst as the apparent reaction order with respect to DMA decreased and the apparent activation energy increased. Finally, this work demonstrates the sensitivity of oxidative coupling reactions to alkali metal promoters and the opportunity to achieve alkali promotion of metal catalysts during SEA synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Foundational insights into the mechanical and molecular evolution of porcine skin gelatin during gelation

Gelatin is a widely used material in biomedical fields, particularly in regenerative medicine and tissue engineering, due to its biocompatibility and versatile properties. While prior research has explored methods to enhance gelatin's mechanical strength and stability, fundamental studies on gelatin, specifically its curing process, mechanical stiffness, and chemical evolution during gelation, remain limited. This study uses ultrasonic testing and Fourier Transform Infrared Spectroscopy (FTIR) to examine gelatin's stiffness and molecular changes during gelation. Samples of 175 and 300 Porcine Skin Bloom Strength Gelatin at concentrations of 2% and 6% (w/v) were analyzed. Through transmission ultrasonic testing helped identify key transition points in gelation, with higher concentrations exhibiting delayed transitions. FTIR revealed that C-N bond formation peaks early while N-H bond deformation persists. A correlation emerged between sound speed and peak absorbance, suggesting that changes in molecular mobility may contribute to the observed sound speed behavior during periods of active bond formation. However, as gelation continues, fewer bonding components may be available, potentially decreasing molecular movement and contributing to the observed increase in sound speed. These findings provide insights into gelatin's mechanical and chemical evolution, offering a framework for improved control over its gelation kinetics. Swept-Frequency Acoustic Interferometry (SFAI) was performed at the end of the curing process to measure the sound speed, enabling the calculation of the bulk moduli of the gelatin samples. The combined use of ultrasonic and FTIR testing provides a non-destructive method for characterizing gelatin and other biomaterials. This approach advances understanding of gelatin curing behavior and supports the development of safer biomaterials with tailored mechanical properties for various applications such as tissue engineering and regenerative medicine.

Biomaterials↗

Pulsed-Potential Electrolysis Enhances Electrochemical C–N Coupling by Reorienting Interfacial Ions

The electrochemical processing of anthropogenic CO 2 is an emerging technology aimed at utilizing renewable energies to synthesize valuable chemicals. Recently, developments in broadening the scope of the CO 2 reduction reaction (CO 2 RR) by enabling heteroatom coupling have surged with a focus on C–N bond formation. Herein, we investigate the factors that govern the selectivity and activity in synthesizing urea from environmentally malignant chemical feedstocks (CO 2 and NO 3 – ). Through a combination of electrolyte optimization and pulsed potential electrolysis, electrochemical urea production was optimized to a Faradaic efficiency of 60.4% with current densities reaching as high as 310 μA cm –2 . This work was further supported by in situ surface enhanced infrared absorbance spectroscopy that reveals the formation of C–N-related species at low overpotentials. Density functional theory calculations revealed that the reaction progresses between early reduction intermediates for the CO 2 RR and NO 3 RR and offered insights into the impacts of pulsed-potential on substrate transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Insights into the Origins of Selectivity in a Cu-Catalyzed C–H Amidation Reaction

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp 3 )-H bonds remains an outstanding challenge. Here, we report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic insights to drive catalytic hydrogenation of formamide intermediates to methanol via deaminative hydrogenation

Amine-promoted hydrogenation of CO 2 to methanol typically proceeds via a formamide intermediate when amines are used as additives or if the hydrogenation is performed in carbon capture solvents. The catalysts used for the hydrogenation of the formamide intermediate dictate the selectivity of the products formed: 1) Deoxygenative hydrogenation (C–O bond cleavage) resulting in N-methylation of amine and deactivation of the solvent, 2) Deaminative hydrogenation (C–N bond cleavage) resulting in formation of methanol and regeneration of the solvent. To date, catalytic reductions of CO 2 with amine promoters suffer from poor selectively for methanol which we attribute to the limiting formamide intermediate, though to date, the conditions that favor C–N cleavage have yet to be fully understood. To better understand the reactivity of the formamide intermediates, a range of heterogenous catalysts were used to study the hydrogenation of formamide. Well-known gas phase CO 2 hydrogenation catalysts catalyze the hydrogenation of formamide to N-methyl product via C–O bond cleavage. However, the selectivity can be readily shifted to selective C–N bond cleavage by addition of an additive with sufficient basicity for both homogenous and heterogeneous catalytic systems. The base additive shifts the selectivity by deprotonating a hemiaminal intermediate formed in situ during the formamide hydrogenation. This prevents dehydration process leading to N-methylated product, which is a key capture solvent deactivation pathway that hinders amine use in carbon capture, utilization, and storage (CCUS). The findings from this study provide a roadmap on how to improve the selectivity of known heterogenous catalysts, enabling catalytic reduction of captured CO 2 to methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical bonding, phase stability and magnetic property in Sm 2 Fe 17 X 3 (X=H, C, N): A first-principles perspective

As a promising alternative to Nd–Fe–B magnets, the critical rare earth free Sm 2 Fe 17 X 3 (X = C, N) exhibits potential for high-performance magnets. However, their poor phase stability remains a major obstacle to developing bulk magnets. We investigated the phase stability and intrinsic magnetic properties of Sm 2 Fe 17 X 3 (X = H, C, N) using first-principles calculations and chemical bond analysis. The formation energies are negative, while the decomposition energies are −1.53, 0.348, and −0.74 eV per formula unit for X = H, C, and N, respectively, which is responsible for the weak thermal stability. Our chemical bond analysis reveals that the bonding asymmetry between Sm–X and Fe–X interactions creates local structural distortions and degrades the phase stability of Sm 2 Fe 17 X 3 . The project Crystal Orbital Hamilton Population (-pCOHP) analysis indicates that the Sm–X bonding remains positive up to the Fermi level, indicating stable bonding interactions. Here, in contrast, the Fe–X bonding becomes negative near the Fermi level, signifying anti-bonding contributions that reduce structural stability. Interstitial atoms X expand the lattice and enhance Fe magnetic moments, but Fe–X bonding suppresses neighboring Fe moments. Electron transfer from Sm to X modifies the valence state of Sm and the crystal field at the site, contributing to enhanced magnetocrystalline anisotropy in Sm 2 Fe 17 X 3 . Among the interstitial elements, carbon and nitrogen—with their larger atomic radius and higher electronegativity—induce greater lattice expansion and form stronger bonds with neighboring Sm and Fe atoms compared to hydrogen. Consequently, Sm 2 Fe 17 X 3 (X = C and N) exhibits better phase stability and significant improvement in magnetic properties.

Chemical bonding↗

Mechanistic Studies of Oxidative Degradation in Diamine-Appended Metal–Organic Frameworks Exhibiting Cooperative CO 2 Capture

Understanding the impact of O 2 during a carbon capture process is vital for designing robust, cost-effective materials for carrying it out. However, mechanistic studies of the O 2 -induced degradation of materials are not easily undertaken owing to the complex sequential reaction pathways that arise. Here, we report comprehensive mechanistic investigations of the O 2 -induced degradation of diamine-appended metal−organic frameworks (MOFs) exhibiting cooperative CO 2 adsorption. Oxygen exposure experiments were performed on seven different diamine-appended MOFs, including e-2−Mg 2 (dobpdc) (e-2 = N-ethylethylenediamine, dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), under various temperatures and O 2 pressures. These experiments show that diamine degradation inhibits CO 2 chemisorption and that the degradation rate is significantly influenced by the diamine structure. In contrast, the parent frameworks remain essentially intact upon O 2 exposure. Detailed characterization of O 2 -exposed e-2−Mg 2 (dobpdc) revealed the formation of various degradation products, including acetaldehyde, carbon dioxide, water, ethylamine, and other aldehyde- and imine-containing species. Together, these observations suggest that diamine degradation occurs via C−N bond cleavage through pathways involving C-centered radicals. Furthermore, computational evaluation of the initiation and propagation pathways for amine degradation in diamine-appended MOFs indicates that (i) degradation is likely initiated by OH • , (ii) carbon-centered radicals generated via radical transfer reactions react with O 2 , leading to amine degradation, and (iii) the ratelimiting step of the degradation reactions likely involves O−O bond cleavage. Overall, these mechanistic insights could inform strategies for mitigating O 2 -induced amine degradation in next-generation carbon capture technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical trends favoring interstitial cluster formation in bcc high-entropy alloys from first-principles calculations

Achieving high strength and ductility is a common goal in structural alloy design. Body-centered cubic high-entropy alloys (HEAs) commonly highlight the conflict between these properties, with stronger alloys being brittle and vice versa. Recent reports suggest interstitial solutes can be used to overcome this trade-off, in some cases providing both strength and ductility enhancements. This effect has been correlated with interstitial cluster formation, although the conditions favoring their formation remain incompletely understood. Using first-principles calculations of solution energies and diffusivities, we provide insights into thermodynamic and kinetic factors favoring interstitial solute clusters. Among C, N and O solutes, O interstitials display most desirable diffusion kinetics. Further, the results highlight the importance of local composition fluctuations in the HEAs to enable the formation of clusters of appreciable size. The results are explained in terms of bonding and distortion trends across solutes and HEA compositions to provide guidelines for alloy design.

Borges, Pedro P P O↗

Divergent Bimetallic Mechanisms in Copper(II)-Mediated C–C, N–N, and O–O Oxidative Coupling Reactions

Copper-catalyzed aerobic oxidative coupling of diaryl imines provides a route for conversion of ammonia to hydrazine. Here the present study uses experimental and density functional theory computational methods to investigate the mechanism of N–N bond formation, and the data support a mechanism involving bimolecular coupling of Cu-coordinated iminyl radicals. Computational analysis is extended to Cu II -mediated C–C, N–N, and O–O coupling reactions involved in the formation of cyanogen (NC–CN) from HCN, 1,3-butadiyne from ethyne (i.e., Glaser coupling), hydrazine from ammonia, and hydrogen peroxide from water. The results reveal two different mechanistic pathways. Heteroatom ligands with an uncoordinated lone pair (iminyl, NH 2 , OH) undergo charge transfer to Cu II , generating ligand-centered radicals that undergo facile bimolecular radical–radical coupling. Ligands lacking a lone pair (CN and CCH) form bridged binuclear diamond-core structures that undergo C–C coupling. This mechanistic bifurcation is rationalized by analysis of spin densities in key intermediates and transition states, as well as multiconfigurational calculations. Radical–radical coupling is especially favorable for N–N coupling owing to energetically favorable charge transfer in the intermediate and thermodynamically favorable product formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward sustainable production of N-containing products via nonthermal plasma-enhanced conversion of natural gas resources

Nonthermal plasmas can directly activate and cleave the strong chemical bonds in molecular nitrogen and methane to facilitate the transformation of these inherently stable molecules through the application of electrical energy. Here, we report a low temperature, atmospheric pressure, nonthermal plasma for the “one-pot” synthesis of olefins, alkynes, higher molecular weight hydrocarbons, ammonia, and nitrogen-containing liquids from a representative shale gas feed enriched with nitrogen. Furthermore, we reproducibly observe a wide range of valuable and synthetically challenging gas-phase and liquid-phase products containing C-N, C-C, and N-H bonding by controlling the N 2 concentration in the inlet feed stream. In nitrogen-lean regimes, hydrocarbon products dominate (e.g., ethylene, acetylene, etc.), while nitrogen-rich regimes promote incorporation of nitrogen into the products, leading to the formation of ammonia and liquid products containing a variety of functionalities (e.g., nitriles, amines, heterocycles). High resolution electrospray ionization mass spectrometry was used to measure molecular weights and identify the chemical formulas of the liquid products. Van Krevelen diagrams were created and showed many products with compositions around H/C = 2 and N/C = 0.5, indicating the potential importance of intermediate species with these ratios for liquid formation (e.g., CH 3 CN + H).

03 NATURAL GAS↗

Mechanistic Studies of an Iron-Catalyzed Intermolecular C–H Amination Reaction under Catalytic Conditions and Having a Large KIE

The conversion of C–H bonds into amines by nitrene insertion is an attractive transformation since it is both atom- and step-economical, and provides a direct route to functionalizing hydrocarbons. Using an iron catalyst [{( tBu pyrr) 2 pyr}Fe(OEt 2 )] (1-OEt 2 ) (( tBu pyrr) 2 pyr 2– = 3,5- t Bu 2 -bis(pyrrolyl)pyridine), we recently demonstrated the catalytic conversion of weak C–H bonds into secondary amines using aryl azides as the nitrene source [Zars, E.; Angew. Chem., Int. Ed. 2023, 62, e202311749]. Here, we describe detailed mechanistic studies of this intermolecular C–H amination reaction under catalytic conditions. We find by Variable Time Normalization Analysis (VTNA) that the conversion of xanthene (2-H 2 ) and 2,4,6-trimethyl-phenyl azide ( Me 3) catalyzed by 1-OEt 2 is an overall 3/2 order process, being 1 st order in 2-H 2 and half order in Me 3. A kinetic isotope effect study (KIE) using 2-d 2 results in a significant decrease in the rate (KIE = 61(15)), which clearly implicates the C–H insertion step as rate-determining. Furthermore, treatment of 1-OEt 2 with one equivalent of N 3 -2,6- i Pr 2 –C 6 H 3 yields the mixed-valence C–N coupled product [( tBu pyrr) 2 pyrFe-N═C(2,6 i Pr 2 –Ph)═N-(2,6 i Pr 2 –Ph))Fe tBu pyrrpyr(2-H-pyrr)] (5 iPr ). Quantum chemical calculations confirm the electronic structure of the mixed-valence dimer in 5 iPr and rationalize the Hammett correlation by a delicate balance in the dinuclearization of the catalytically active monomers. Calculations further indicate significant tunneling for the pivotal H atom abstraction by the iron-imidyl complex. Combining all these results allows us to propose a mechanism consisting of imido formation in equilibrium with a radical-coupled diiron system, followed by stepwise C–H insertion via a linear H atom abstraction transition state and subsequent radical rebound.

azides↗

Surveying Phase Modifier Functional Groups for Applications to Ln(III) Separations

The application of N,N,N',N'-tetraoctyl diglycolamide (TODGA) in solvent extraction systems for lanthanide (Ln) separations is well understood. In these systems, the formation of a third phase has motivated the use of phase modifiers to enable higher concentrations of H + and Ln common to industrial processes. Several different phase modifiers with applications to diglycolamide (DGA) systems have previously been reported, with a focus on tri-n-butyl phosphate (TBP), N,N'-dihexylactanamide (DHOA), N,N-dioctyl-2-hydroxyacetamide (DOHyA), N,N'-dimethyl-N,N'-dioctylhexylethoxy malonamide (DMDOHEMA), and octanol. While the primary utility of phase modifiers is the increased metal loading, they can have significant effects on the metal distribution ratios, which are well described by the energetics of the extraction process itself. However, the mechanisms by which phase modifiers impact distribution ratios are not generally understood. This work considers the ability of phase modifiers to affect Ln distribution ratios by using phase modifiers with two different functional groups (–Cl and –C≡N) and an octyl alkyl chain in a TODGA and n-dodecane system. Determining the effect of chlorooctane and octane nitrile is important for understanding how phase modifier functional groups and their hydrogen bonding interactions affect Ln extraction. Through combining distribution ratio measurements with organic phase spectroscopic investigations, the impact of chlorooctane and octane nitrile on Ln extraction and their inner-sphere complexes is reported. The addition of either chlorooctane or octane nitrile to TODGA in n-dodecane decreases Ln extraction while maintaining the same inner-sphere Ln complex. The lack of change in inner-sphere Ln-TODGA coordination upon incorporation of phase modifiers and the significant impact of these phase modifiers on distribution ratios suggest the importance of a supramolecular structure. Understanding the role of chlorooctane and octane nitrile on the organic phase structure at longer length scales has been identified as an avenue for future investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of 9.5 years warming on SOC concentration and composition in bulk soil and density fractions

Original data of whole-soil warming experiment after 9.5 years at Blodgett Forest Research Station. The Blodgett Forest is a mixed coniferous temperate forest with Mediterranean climate. The annual air temperature is 12.5℃ and the annual precipitation is 1774 mm yr-1- The soil is mesic ultic Alfisol of granitic origin, equivalent to Dystric Cambisol according to The World Reference Base for Soil Resources (WRB) system. The soil is warmed down to 1 m at + 4℃ by vertically installed heating cables. At the time of soil sampling on 1 May 2023, the whole-soil warming experiment had been running for approximately 9.5 years, from January 2014 to May 2023. The dataset includes: - Bulk_EA: C, N content, δ13C, and CN ratio of bulk soil; - Density_fractionation: organic carbon concentration, δ13C, and C/N ratio of free light fraction (fLF), occluded ligh fraction (oLF), and heavy fraction (HF); - PCA_DRIFT_AUC: original data of area under the curve (AUC) values of eight carbon bond types integrated on diffuse reflectance infrared fourier transform spectroscopy for each soil sample and soil fraction, which are consequently used for principal component analysis (PCA); - DRIFTS_stability_index: the calculation of aliphatic C–H (3000–2800 cm-1) to aromatic C=C (1670–1600 cm-1) ratios for each bulk soil sample and soil fraction. All data are provided in CSV format and can be viewed using Microsoft Excel.

Climate change↗

Chemical Evolution of Interstellar Dust into Planetary Materials

Comets are believed to retain some interstellar materials, stored in fairly pristine conditions since-their formation. The composition and properties of cometary dust grains should reflect those of grains in the outer part of the protosolar nebula which, at least in part, were inherited from the presolar molecular cloud. However, infrared emission features in comets differ from their interstellar counterparts. These differences imply processing of interstellar material on its way to incorporation in comets, but C and N appear to be retained. Overall dust evolution from the interstellar medium (ISM) to planetary materials is accompanied by an increase in proportion of complex organics and a decrease in pure carbon phases. The composition of cometary dust grains was measured in situ during fly-by missions to comet Halley in 1986. The mass spectra of about 5000 cometary dust grains with masses of 5 x 10(exp -17) - 5 x 10(exp -12) g provide data about the presence and relative abundances of the major elements H, C, N, O,Na, Mg, Al, Si, S, Cl, K, Ca, Ti, Cr, Fe, Ni. The bulk abundances of major rock-forming elements integrated over all spectra were found to be solar within a factor of 2, while the volatile elements H, C, N, O in dust are depleted in respect to their total cosmic abundances. The abundances of C and N in comet dust are much closer to interstellar than to meteoritic and are higher than those of dust in the diffuse ISM. In dense molecular clouds dust grains are covered by icy mantles, the average composition of which is estimated to be H:C:N:O = 96:14:1:34. Up to 40% of elemental C and O may be sequestered in mantles. If we use this upper limit to add H, C, N and O as icy mantle material to the abundances residing in dust in the diffuse ISM, then the resulting values for H. C, and N match cometary abundances. Thus, ice mantles undergoing chemical evolution on grains in the dense ISM appear to have been transformed into less volatile and more complex organic residues wherein the H, C and N are largely retained and ultimately accreted in cometary dust. The abundance of O is about the same for cometary dust, meteorites and interstellar dust. In all these samples, most of O in a solid phase is bonded to silicates. In dense molecular clouds, the abundance of O in dust+mantles is significantly higher then in cometary dust. This difference may reflect the greater lability of oxygenated species toward astrophysical processing. Laboratory studies show that O-bearing functional groups in organic compounds tend to be relatively easily removed by heating and/or UV and particle irradiation . In Halley's coma, O-containing organic grains, being unstable, were located closest to the nucleus. The decomposition of the organic grain component in the coma provided a significant extended source contribution to O-containing gaseous species such as CO and H2CO.

Fomenkova, M. N.↗

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗