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The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition, and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalystsâin which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivityâare particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag, and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. The integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.
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Aleaciones , Óxidos , Catálisis , Dominio Catalítico , Metales , Oxidación-Reducción , Óxidos/químicaRESUMEN
The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.
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ConspectusThe abundance of cheap, natural gas has transformed the energy landscape, whereby revealing new possibilities for sustainable chemical technologies or impacting those that have relied on traditional fossil fuels. The primary component, methane, is underutilized and wastefully exhausted, leading to anthropogenic global warming. Historically, the manipulation of methane remained "clavis aurea," an insurmountable yet rewarding challenge and thus the focus of intense research. This is primarily due to an inability to dissociate C-H bonds in methane selectively, which requires a high energy penalty and is an essential prerequisite for the direct conversion of methane into a large set of value-added products. The discovery of such processes would promise an energy gainful use of natural gas benefiting several essential chemical processes associated with C1 chemistry. This first C-H bond dissociation step of the methane molecule appears in numerous catalytic mechanisms as the rate-determining step or most essential barrier sequence for all subsequent steps that follow in the production of C-C, C-O, or Cx-Hy-Oz bonds found in value added products. A main goal is to catalytically reduce the energy barrier for the first C-H bond dissociation to be able to achieve the activation of methane at low or moderate temperatures. As such there is great value in understanding the fundamental nature of the active sites responsible for bond breaking or formation and thus be able to facilitate better control of this chemistry, leading to the development of new technologies for fuel production and chemical conversion. Surface science studies offer enhanced perspectives for a careful manipulation of bonds over the last layer atoms of catalyst surfaces, an essential factor for the design of atomically precise catalysts and unravelling of the reaction mechanism. With the advent of new surface imaging, spectroscopy, and in situ tools, it has been possible to decipher the surface chemistry of complex materials systems and further our understanding of atomic active sites on the surfaces of metals, oxides, and carbides or metal-oxide and metal-carbide interfaces. The once considered near impossible step of C-H bond activation is now observed at low temperatures with high propensity over a collection of oxide, metal-oxide, and metal-carbide systems in a conventional or inverse configuration (oxide or carbide on metal). The enabling of C-H activation at low temperature has opened interesting possibilities for the specific production of chemicals such as methanol directly from methane, a step toward facile synthesis of liquid fuels. We highlight the most recent of these results and present the key aspects of active site configurations engineered from surface science studies which enable such a simple reactive event through careful manipulation of the last surface layer of atoms found in the catalyst structure. New concepts which help in the activation and conversion of methane are discussed.
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A single atom Ti-Cu(111) surface alloy can be generated by depositing small amounts of Ti onto Cu(111) at slightly elevated surface temperatures (â¼500 to 600 K). Scanning tunneling microscopy shows that small Ti-rich islands covered by a Cu single layer form preferentially on ascending step edges of Cu(111) during Ti deposition below about 400 K but that a Ti-Cu(111) alloy replaces these small islands during deposition between 500 and 600 K, producing an alloy in the brims of the steps. Larger partially Cu-covered Ti-containing islands also form on the Cu(111) terraces at temperatures between 300 and 700 K. After surface exposure to CO at low temperatures, reflection absorption infrared spectroscopy (RAIRS) reveals distinct C-O stretch bands at 2102 and 2050 cm-1 attributed to CO adsorbed on Cu-covered Ti-containing domains vs sites in the Ti-Cu(111) surface alloy. Calculations using density functional theory (DFT) suggest that the lower frequency C-O stretch band originates specifically from CO adsorbed on isolated Ti atoms in the Ti-Cu(111) surface alloy and predicts a higher C-O stretch frequency for CO adsorbed on Cu above subsurface Ti ensembles. DFT further predicts that CO preferentially adsorbs in flat-lying configurations on contiguous Ti surface structures with more than one Ti atom and thus that CO adsorbed on such structures should not be observed with RAIRS. The ability to generate a single atom Ti-Cu(111) alloy will provide future opportunities to investigate the surface chemistry promoted by a representative early transition metal dopant on a Cu(111) host surface.
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We investigated the growth and auto-oxidation of Pd deposited onto a AgOx single-layer on Ag(111) using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Palladium initially grows as well-dispersed, single-layer clusters that adopt the same triangular shape and orientation of Agn units in the underlying AgOx layer. Bi-layer clusters preferentially form upon increasing the Pd coverage to â¼0.30 ML (monolayer) and continue to develop until aggregating and forming a nearly conformal Pd bi-layer at a coverage near 2 ML. Analysis of the STM images provides quantitative evidence of a transition from single to bi-layer Pd growth on the AgOx layer, and a continuation of bi-layer growth with increasing Pd coverage from â¼0.3 to 2 ML. XPS further demonstrates that the AgOx layer efficiently transfers oxygen to Pd at 300 K, and that the fraction of Pd that oxidizes is approximately equal to the local oxygen coverage in the AgOx layer for Pd coverages up to at least â¼0.7 ML. Our results show that oxygen in the initial AgOx layer mediates the growth and structural properties of Pd on the AgOx/Ag(111) surface, enabling the preparation of model PdAg surfaces with uniformly distributed single or bi-layer Pd clusters. Facile auto-oxidation of Pd by AgOx further suggests that oxygen transfer from Ag to Pd could play a role in promoting oxidation chemistry of adsorbed molecules on PdAg surfaces.
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Transcatheter aortic valves (TAV) are symmetrically designed, but they are often not deployed inside cylindrical conduits with circular cross-sectional areas. Many TAV patients have heavily calcified aortic valves, which often result in deformed prosthesis geometries after deployment. We investigated the effects of deformed valve annulus configurations on a surgical bioprosthetic valve as a model for TAV. We studied valve leaflet motions, stresses and strains, and analog hydrodynamic measures (using geometric methods), via finite element (FE) modeling. Two categories of annular deformations were created to approximate clinical observations: (1) noncircular annulus with valve area conserved, and (2) under-expansion (reduced area) compared to circular annulus. We found that under-expansion had more impact on increasing stenosis (with geometric orifice area metrics) than noncircularity, and that noncircularity had more impact on increasing regurgitation (with regurgitation orifice area metrics) than under-expansion. We found durability predictors (stress/strain) to be the highest in the commissure regions of noncircular configurations such as EllipMajor (noncircular and under-expansion areas). Other clinically relevant performance aspects such as leaflet kinematics and coaptation were also investigated with the noncircular configurations. This study provides a framework for choosing the most challenging TAV deformations for acute and long-term valve performance in the design and testing phase of device development.
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Prótesis Valvulares Cardíacas , Válvula Aórtica , Benchmarking , HumanosRESUMEN
We used temperature programmed desorption (TPD) and low energy electron diffraction (LEED) to investigate the isomeric structural transformation of a Tb2O3 thin film grown on Pt(111). We find that repeated oxidation and thermal reduction to 1000 K transforms an oxygen-deficient, cubic fluorite (CF) Tb2O3(111) thin film to the well-defined bixbyite, or c-Tb2O3(111) structure, whereas annealing the CF-Tb2O3(111) film in UHV is ineffective in causing this structural transformation. We estimate that the final stabilized film consists of about ten layers of c-Tb2O3(111) in the surface region plus about eight layers of CF-Tb2O3(111) located between the c-Tb2O3(111) and the Pt(111) substrate. Our measurements reveal the development of two distinct O2 TPD peaks during the CF to bixbyite transformation that arise from oxidation of c-Tb2O3 domains to the stoichiometrically-invariant ι-Tb7O12 and δ-Tb11O20 phases and demonstrate that the c-Tb2O3 phase oxidizes more facilely than CF-Tb2O3. We present evidence that nucleation and growth of c-Tb2O3 domains occurs at the buried TbOx/CF-Tb2O3 interface, and that conversion of the interfacial CF-Tb2O3 to bixbyite takes place mainly during thermal reduction of TbOx above â¼900 K and causes newly-formed c-Tb2O3 to advance deeper into the film. The avoidance of low Tb oxidation states may facilitate the CF to bixbyite transformation via this redox mechanism.
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Crevice corrosion is one of the major mechanisms that drives implant failure in orthopedic devices that have modular interfaces. Despite the prevalence of crevice corrosion in modular interfaces, very little is known with regards to the susceptibility of different material combinations to participate in crevice corrosion. In this study, we compare two electrochemical methods, ASTM F2129, Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements to Determine the Corrosion Susceptibility of Small Implant Devices, and a modified version of ASTM F746, Standard Test Method for Pitting or Crevice Corrosion of Metallic Surgical Implant Materials, in their ability to induce crevice corrosion. Four commonly used metals, 316 stainless steel, commercially pure titanium (Ti grade 2), Ti-6Al-4V (Ti grade 5), and cobalt-chromium-molybdenum per ASTM F1537, Standard Specification for Wrought Cobalt-28Chromium-6Molybdenum Alloys for Surgical Implants (UNSR31537, UNSR31538, and UNSR31539), were used to form crevices with a rod and washer combination. As a control, the metal rod materials were tested alone in the absence of crevices using ASTM F2129 and the modified ASTM F746 method. As another control to determine if crevices formed with polymeric materials would influence crevice corrosion susceptibility, experiments were also conducted with metal rods and polytetrafluorethylene washers. Our results revealed more visible corrosion after ASTM F2129 than ASTM F746. Additionally, ASTM F746 was found to falsely identify crevice corrosion per the critical pitting potential when visual inspection found no evidence of crevice corrosion. Hence, ASTM F2129 was found to be more effective overall at evaluating crevice corrosion compared to ASTM F746.
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Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO2(110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO2(110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to COx species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO2(110) during TPRS. Partial hydrogenation of the IrO2(110) surface is found to enhance ethylene production from ethane while suppressing oxidation to COx species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO2(110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO2(110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.
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We investigated the adsorption and oxidation of n-propane and cyclopropane (C3H8 and c-C3H6) on the IrO2(110) surface using temperature programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. We find that the activation of both C3H8 and c-C3H6 is facile on IrO2(110) at low temperature, and that the dissociated alkanes oxidize during TPRS to produce CO, CO2 and H2O above â¼400 K. Propane conversion to propylene is negligible during TPRS for the conditions studied. Our results show that the maximum yield of alkane that oxidizes during TPRS is higher for c-C3H6 compared with C3H8 (â¼0.30 vs. 0.18 monolayer) and that pre-hydrogenation of the surface suppresses c-C3H6 oxidation to a lesser extent than C3H8. Consistent with the experimental results, DFT predicts that C3H8 and c-C3H6 form σ-complexes on IrO2(110) and that C-H bond activation of the complexes as well as subsequent dehydrogenation are highly facile via H-transfer to Obr atoms (bridging O-atoms). Our calculations predict that propane conversion to gaseous propylene is kinetically disfavored on IrO2(110) because HObr recombination makes Obr atoms available to promote further dehydrogenation at lower temperatures than those needed for the adsorbed C3H6 intermediate to desorb as propylene. We also present evidence that that the ability for c-C3H6 to activate via ring-opening is responsible for cyclopropane attaining higher reaction yields during TPRS and exhibiting a weaker sensitivity to surface pre-hydrogenation compared with n-propane.
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We used temperature-programmed reaction spectroscopy (TPRS) to investigate the adsorption and oxidation of methanol on stoichiometric and O-rich RuO2(110) surfaces. We find that the complete oxidation of CH3OH is strongly preferred on stoichiometric RuO2(110) during TPRS for initial CH3OH coverages below â¼0.33 ML (monolayer), and that partial oxidation to mainly CH2O becomes increasingly favored with increasing CH3OH coverage from 0.33 to 1.0 ML. We present evidence that an adsorbed CH2O2 species serves as the key intermediate to complete oxidation and that CH2O2 formation is intrinsically facile but becomes limited by the availability of bridging O-atoms on stoichiometric RuO2(110) at initial CH3OH coverages above 0.33 ML. We show that methanol molecules adsorbed in excess of 0.33 ML dehydrogenate to mainly CH2O and desorb during TPRS, with adsorbed CH3O groups mediating the evolution of both CH2O and CH3OH. We find that O-rich RuO2(110) surfaces are also highly active toward methanol oxidation and that selectivity toward the complete oxidation of methanol increases markedly with increasing coverage of on-top O-atoms (Oot) on RuO2(110). Our results demonstrate that CH3OH species adsorbed within Oot-rich domains react efficiently during TPRS, in parallel with reaction of CH3OH adsorbed initially on cus-Ru sites. The data suggests that the facile hydrogenation of Oot atoms and the resulting desorption of H2O at low-temperature (<â¼400 K) provides an efficient pathway for restoring reactive O-atoms and thereby promoting complete oxidation of methanol on the O-rich RuO2(110) surface.
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Metal oxide films can form on late transition-metal catalysts under sufficiently oxygen-rich conditions, and typically cause significant changes in the catalytic performance of these materials. Several investigations using sensitive in situ surface characterization techniques reveal that the CO oxidation activity of Pd and other late transition-metal catalysts increases abruptly under conditions at which metal oxide structures begin to develop. Findings such as these provide strong motivation for developing atomic-scale descriptions of oxidation catalysis over oxide films of the late transition-metals. Surface oxygen vacancies can play a central role in mediating oxidation catalysis promoted by metal oxides. In general, adsorbed reactants abstract oxygen atoms from the lattice of the oxide surface, thereby creating oxygen vacancies, while gaseous O2 replenishes the reactive surface oxygen atoms and eliminates oxygen vacancies. Oxygen vacancies also represent a distinct type of surface site on which the binding and reactivity of adsorbed species can differ compared with sites on the pristine oxide surface. Detailed characterization of vacancy-mediated rate processes is thus essential for developing reliable mechanistic descriptions of oxidation catalysis over reducible metal oxide films. Careful measurements performed in ultrahigh vacuum (UHV) using well-defined oxide surfaces in combination with molecular simulations afford the capability to isolate and characterize such reaction steps, and thus provide information that is needed for developing mechanistic models of oxidation catalysis over metal oxides. In this Account, we discuss vacancy-mediated processes that are involved in the oxidation of CO on the PdO(101) surface as determined from UHV surface science experiments and density functional theory (DFT) calculations. These studies show that CO binds strongly on Pd atoms that are located next to surface oxygen vacancies, and diffuses rapidly to these sites during reduction of the oxide surface by CO. The enhanced binding also raises the energy barriers for desorption and oxidation of CO, but the difference in these barriers remains nearly identical to that for CO adsorbed on the pristine PdO(101) surface. These recent studies also show that oxygen from the subsurface efficiently eliminates surface oxygen vacancies during CO oxidation at temperatures as low as 400 K, and thereby reveal a facile pathway by which PdO(101) surface domains can be maintained during oxide reduction.
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We investigated the molecular adsorption of methane, ethane, propane and n-butane on stoichiometric and oxygen-rich RuO2(110) surfaces using temperature-programmed desorption (TPD) and dispersion-corrected density functional theory (DFT-D3) calculations. We find that each alkane adsorbs strongly on the coordinatively-unsaturated Ru (Rucus) atoms of s-RuO2(110), with desorption from this state producing a well-defined TPD peak at low alkane coverage. As the coverage increases, we find that alkanes first form a compressed layer on the Rucus atoms and subsequently adsorb on the bridging O atoms of the surface until the monolayer saturates. DFT-D3 calculations predict that methane preferentially adsorbs on top of a Rucus atom and that the C2 to C4 alkanes preferentially adopt bidentate configurations in which each molecule aligns parallel to the Rucus atom row and datively bonds to neighboring Rucus atoms. DFT-D3 predicts binding energies that agree quantitatively with our experimental estimates for alkane σ-complexes on RuO2(110). We find that oxygen atoms adsorbed on top of Rucus atoms (Oot atoms) stabilize the adsorbed alkane complexes that bind in a given configuration, while also blocking the sites needed for σ-complex formation. This site blocking causes the coverage of the most stable, bidentate alkane complexes to decrease sharply with increasing Oot coverage. Concurrently, we find that a new peak develops in the C2 to C4 alkane TPD spectra with increasing Oot coverage, and that the desorption yield in this TPD feature passes through a maximum at Oot coverages between â¼50% and 60%. We present evidence that the new TPD peak arises from C2 to C4 alkanes that adsorb in upright, monodentate configurations on stranded Rucus sites located within the Oot layer.
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Ultrathin metal oxides exhibit unique chemical properties and show promise for applications in heterogeneous catalysis. Monolayer FeO films supported on metal surfaces show large differences in reactivity depending on the metal substrate, potentially enabling tuning of the catalytic properties of these materials. Nitric oxide (NO) adsorption is facile on silver-supported FeO, whereas a similar film grown on platinum is inert to NO under similar conditions. Abâ initio calculations link this substrate-dependent behavior to steric hindrance caused by substrate-induced rumpling of the FeO surface, which is stronger for the platinum-supported film. Calculations show that the size of the activation barrier to adsorption caused by the rumpling is dictated by the strength of the metal-oxide interaction, offering a straightforward method for tailoring the adsorption properties of ultrathin films.
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Advances in the fundamental understanding of alkane activation on oxide surfaces are essential for developing new catalysts that efficiently and selectively promote chemical transformations of alkanes. In this tutorial review, we discuss the current understanding of alkane activation on crystalline metal oxide surfaces, and focus mainly on summarizing our findings on alkane adsorption and C-H bond cleavage on the PdO(101) surface as determined from model ultrahigh vacuum experiments and theoretical calculations. These studies show that alkanes form strongly-bound σ-complexes on PdO(101) by datively bonding with coordinatively-unsaturated Pd atoms and that these molecularly adsorbed species serve as precursors for C-H bond activation on the oxide surface. In addition to discussing the binding and properties of alkane σ-complexes on PdO(101), we also summarize recent advances in kinetic models to predict alkane dissociation rates on solid surfaces. Lastly, we highlight computations which predict that the formation and facile C-H bond activation of alkane σ-complexes also occurs on RuO2 and IrO2 surfaces.
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Achieving selective C-H bond cleavage is critical for developing catalytic processes that transform small alkanes to value-added products. The present study clarifies the molecular-level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C-H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ-complexes preferentially adopt geometries on PdO(101) in which only primary C-H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H-Pd dative bond forms at each CH3 group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C-H bonds.
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A multistage clustering and data processing method, SWIFT (detailed in a companion manuscript), has been developed to detect rare subpopulations in large, high-dimensional flow cytometry datasets. An iterative sampling procedure initially fits the data to multidimensional Gaussian distributions, then splitting and merging stages use a criterion of unimodality to optimize the detection of rare subpopulations, to converge on a consistent cluster number, and to describe non-Gaussian distributions. Probabilistic assignment of cells to clusters, visualization, and manipulation of clusters by their cluster medians, facilitate application of expert knowledge using standard flow cytometry programs. The dual problems of rigorously comparing similar complex samples, and enumerating absent or very rare cell subpopulations in negative controls, were solved by assigning cells in multiple samples to a cluster template derived from a single or combined sample. Comparison of antigen-stimulated and control human peripheral blood cell samples demonstrated that SWIFT could identify biologically significant subpopulations, such as rare cytokine-producing influenza-specific T cells. A sensitivity of better than one part per million was attained in very large samples. Results were highly consistent on biological replicates, yet the analysis was sensitive enough to show that multiple samples from the same subject were more similar than samples from different subjects. A companion manuscript (Part 1) details the algorithmic development of SWIFT.
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Algoritmos , Células Sanguíneas/citología , Análisis por Conglomerados , Citometría de Flujo/métodos , Antígenos/sangre , Antígenos/inmunología , Células Sanguíneas/inmunología , Linaje de la Célula , Biología Computacional , Humanos , Distribución Normal , Linfocitos T/citología , Linfocitos T/inmunologíaRESUMEN
Fused Granular Fabrication Additive Manufacturing (FGF AM) has the capability to create tooling that is lower cost than conventionally manufactured tooling and still has sufficient properties for many applications. A vacuum infusion (VI) mold was printed from fiberglass-acrylonitrile butadiene styrene (ABS) and evaluated for wear and suitability for small VI runs. The mold was designed to accentuate high wear as a "worst case" scenario. The mold was able to produce 10 parts successfully before any noticeable change occurred to the surface finish. By 14 parts, the surface finish had roughened sufficiently that demolding was difficult and resulted in damage to the part. Profilometry measurements showed a 7 × increase in roughness over the run. No significant tool wear or change in geometry was detected. Even longer life would be expected for typical tooling designs since the test mold was deliberately designed to accentuate wear and demolding issues. Based on these results, similar FGF molds are a feasible option for short run VI production for prototyping or low-volume composites manufacturing, possibly at lower cost and quicker turnaround time than machined aluminum molds.
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BACKGROUND: Rosai-Dorfman disease (RDD) is a rare, nonmalignant histiocytosis. It typically occurs in lymph nodes, skin, and soft tissues, but numerous reports of central nervous system involvement exist in the literature. The peripheral nervous system has rarely been involved. In this study, the authors present a case of RDD isolated to the cauda equina. The presentation, management, surgical technique, and adjunctive treatment strategy are described. OBSERVATIONS: A 31-year-old female presented with 6 months of progressive left lower-extremity numbness involving the lateral aspect of the foot and weakness of the left toes. Magnetic resonance imaging of the lumbar spine demonstrated a homogeneously enhancing intradural lesion involving the cauda equina at the L2-3 levels. Histopathology after resection revealed a histiocytic infiltrate, positive for CD68 and S100, and emperipolesis consistent with RDD. No adjuvant therapy was administered, and the patient had full remission at the 1-year follow-up. Only five other cases of intradural RDD lesions of the cauda equina have been reported in the literature. LESSONS: RDD of the cauda equina is an especially rare and challenging diagnosis that can mimic other dura-based lesions, such as meningiomas. A definitive diagnosis of RDD relies on pathognomonic histopathological and immunohistochemical findings.
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Reaction products in heterogeneous catalysis can be detected either on the catalyst surface or in the gas phase after desorption. However, if atoms are dissolved in the catalyst bulk, then reaction channels can become hidden. This is the case if the dissolution rate of the deposits is faster than their formation rate. This might lead to the underestimation or even overlooking of reaction channels such as, e.g., carbon deposition during hydrocarbon oxidation reactions, which is problematic as carbon can have a significant influence on the catalytic activity. Here, we demonstrate how such hidden deposition channels can be uncovered by carefully measuring the product formation rates in the local gas phase just above the catalyst surface with time-resolved ambient pressure X-ray photoelectron spectroscopy. As a case study, we investigate methane oxidation on a polycrystalline Pd catalyst in an oxygen-lean environment at a few millibar pressure. By ramping the temperature between 350 and 525 °C, we follow the time evolution of the different reaction pathways. Only in the oxygen mass-transfer limit do we observe CO production, while our data suggests that carbon deposition also happens outside this limit.