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To understand how the composition of novel lubricant additives and their ash interact with gasoline particulate filters (GPFs), an accelerated aging protocol was conducted using three lubricant additive formulations and two GPF types. The additive packages (adpaks) consisted of Ca+Mg detergent in a 3:1 or 0:1 ratio and an anti-wear component—either zinc dialkyl dithiophosphate (ZDDP) or a novel phosphonium-phosphinate ionic liquid (IL) substitute. The particulate sampling captured amount/compositions of particulate matter (PM) generated, total particulate number, and size distribution. Five ash loadings were completed. GPF position and adpak composition affected the backpressure, ash composition, ash morphology, and captured mass. The particulate sampling indicated that the ash component consisted primarily of particles less than 50 nm in size and that the Mg-only adpak resulted in more particulate of 50–400 nm in size. Postmortem materials characterization indicated GPFs in the underfloor position had deeper penetration of ash into the walls compared to the close-coupled position. Additionally, the Mg-only adpak had a higher filter collection efficiency (>90%) and the ash particles consisted of a higher concentration of dense ash material. In contrast, four of the 3:1 Ca:Mg lubricant adpaks resulted in a collection efficiency of only 40–50%. Although the collection efficiency was higher with the Mg-only adpak, the ash layer in the GPF was not thicker, nor was the penetration into the wall more significant, and surprisingly the full useful life (FUL) backpressure was lower than with Ca:Mg adpaks. The higher density of the Mg-derived ash was the only detectable difference. A possible explanation of this observation is that Mg ash has a lower melting point and is more susceptible to densification during combustion or GPF regeneration. The substitution of IL in place of the ZDDP did not lead to any notable changes in collection efficiency or location of the ash.

The chemical and structural stability of two commercial multicomponent silicate glasses (SCN and G6) in contact with yttria-stabilized zirconia (YSZ) was investigated after exposure times of up to 40,000 hours in air at 800 °C. With exposure time, interfacial layers develop at the SCN-YSZ and G6-YSZ interfaces, which were characterized in detail using both quantitative chemical analysis and atomic-resolution imaging. At the SCN-YSZ interface, a Ca-Ba-Si-O reaction phase was found to grow by diffusion control. In G6-YSZ, Raman spectroscopy and electron microscopy revealed a disorganized interfacial reaction later between G6 and YSZ, and the occurrence of cubic to tetragonal to monoclinic phase transformations in YSZ. This microstructural evolution is discussed in terms of devitrification resistance of glass and diffusion processes at interfaces.

Creep-rupture behavior and microstructural response in alumina-forming austenitic (AFA) alloys with two different precipitation strengthening mechanisms, “Laves-phase + M23C6 carbide” and “coherent L12 γ′-Ni3(Al,Ti),” were explored as “model” cases of multi-phase, multi-scale heat-resistant AFA alloys for 650–750°C use. These alloys will be used to guide and verify computational alloy design and life-prediction modeling under an on-going eXtremeMAT project through the Office of Fossil Energy and Carbon Management, US Department of Energy. Computational thermodynamics were used to design and predict the amounts of strengthening and deteriorating secondary phases at 750°C. Creep-rupture lives of the alloys tested at 750°C and 100 MPa were in a range of 4000–9000 h, and the microstructure at the gage/grip after creep-rupture testing was compared with isothermally aged alloys for 1500 h, as well as the calculated phases. Detailed microstructure characterization includes phase identification, volume fraction measurement, and compositional analysis, which were correlated with the creep-rupture properties. High-temperature oxidation resistance was also screened and compared with commercial, chromia-forming heat-resistant steels. These model alloys also provide the basis for further design and optimization of next generation AFA alloys with improved creep resistance.

Silver and palladium ion-exchanged BEA zeolites (Si/Al = 12.5) and silver ion-exchanged ZSM-5 zeolites (Si/Al = 15) were studied for their ability to adsorb and desorb propylene and NO under simulated diesel exhaust conditions. The adsorption experiment results demonstrated the excellent ability of bare BEA zeolites to adsorb propylene, but only a small amount of NO. The presence of H2O inhibited the adsorption of both C3H6 and NO. Ion-exchanging BEA zeolites with Ag (1.2 and 5.1 wt.% Ag/BEA) attenuated the inhibiting effect of H2O on C3H6 adsorption, while NO storage remained inhibited. Adsorption experiments indicated that C3H6 and NO competed with each other for Pd sites with C3H6 showing stronger adsorption compared to NO, whereas Ag sites preferentially adsorbed C3H6. DRIFTS data indicated the formation of nitrate, formate and acetate species on Ag and Pd, while C3H6 and NO adsorption was also observed on the zeolite hydroxyl groups in the absence of H2O. However, the C3H6 and NO adsorption on the zeolite hydroxyl groups was significantly inhibited in the presence of H2O. Additionally, nitrosyl, acrolein and carbonate species were formed over 1.0 wt.% Pd/BEA. The effluent analysis during the temperature-programmed desorption in the DRIFTS reactor revealed that adsorbed C3H6 and NO reacted during the release to form oxidation reaction byproducts. The 1.0 wt.% Pd/BEA zeolite showed the greatest oxidation ability during desorption with the majority of stored C3H6 converted to CO2.

Concentrating solar power plant designers are interested in supercritical CO2 (sCO2) for the power block to achieve > 50% electrical efficiency at > 700 °C. The goal of this project was to develop a long-term (> 100 kh) lifetime model for sCO2 compatibility using 10–15 kh laboratory exposures. Three Ni-based alloys (625, 282 and 740H) and an advanced austenitic stainless steel were evaluated in long-term exposures at 700–800 °C using 500-h cycles in laboratory air, 0.1 MPa industrial grade (IG) CO2 and 30 MPa supercritical IG CO2 and using 10-h cycles in 0.1 MPa IG CO2 and O2. Mass change data and quantification of the oxide scale thickness and depth of internal attack after 1000–10,000 h exposures at 750 °C indicate that these materials are compatible with the sCO2 environments with modeling used to predict long-term behavior. Comparison of the 0.1 and 30 MPa 500-h cycle results did not show a significant effect of pressure on the reaction, and no significant internal carburization was observed under these conditions, even for the stainless steel, suggesting that chromia scales may be better C diffusion barriers than expected. For the Ni-based alloys, thermal cycling to simulate the solar duty cycle did not result in scale spallation after 15 kh in 10-h cycles or 4 kh in 1-h cycles at 750 °C. However, the stainless steel specimens formed an Fe-rich oxide after ~ 1500-h cumulative exposure time in both 1- and 10-h cycles.

Plastic-based gamma-ray detector materials such as polyvinyl toluene (PVT) occasionally suffer from loss of optical light transmission due to internal defects or “fogging” when exposed to some environmental conditions over time. Fogging results in reduced scintillation light propagated to the photomultiplier tube for collection. Investigations of the physical cause of these defects and their associated environmental conditions are ongoing. The goal of this article was to characterize the signs and effects of fogging over a simulated 22-year lifespan of the PVT in outdoor environments. Two potential mitigation methods were also evaluated, and one successfully mitigated the phenomena.

As part of round robin testing, specimens of commercial alloys 316, 120, 625, and 740 were exposed to 20 MPa research grade CO2 at 700 °C for up to 1500 h. The first set of specimens had higher mass gain likely due to impurities not flushed from the autoclave at startup. After this issue was corrected, an identical set of specimens exhibited lower mass gains for both the Fe- and Ni-based alloys. The differences in reaction products were characterized to understand the effect of impurities under these conditions. As suggested by the mass change, thicker oxides were formed in each case, primarily for the Fe-based alloys. For the Ni-based alloys, the difference was primarily in the transient stage of oxidation with no change in rate constant. Alloy 120 exhibited increased internal attack, and differences in the scale phases formed were characterized to better understand the effect of impurities. Alloy 740 primarily exhibited a greater depth of internal attack in the first run.

Boron containing catalysts have great potential in the oxidative dehydrogenation of propane. Herein, a series of 15, 25 and 42 at% boron-hyperdoped silicon catalysts synthesized by laser pyrolysis was studied. Boron-hyperdoped silicon samples showed >6 times higher propylene productivity than commercial h-BN at 450 °C.

In-situ formation of ZrB2–SiC composites was investigated by reactive spark plasma sintering of precursor powders according to the reaction B4C + 2ZrC + 3Si → 3SiC + 2ZrB2. The reaction and process presented here involves a diffusion reaction between B4C and ZrC which facilitates the formation of ZrB2, while liquid phase sintering of silicon facilitates atomic diffusion and combines with free C from the B4C and ZrC reaction to form SiC within minutes of heating and there were some residual unreacted precursor materials. An interpenetrating matrix of ZrB2–SiC was formed that shows increased fracture toughness (6.03 ± 0.45 MPa m1/2) despite relatively low density (95 %).

Metallic alloy bond coats are used as an interlayer to promote adhesion of ceramic Thermal Barrier Coatings (TBCs) to the superalloy substrates. These bond coats can be applied through a variety of processing means such as Air Plasma Spray (APS), High-Velocity Oxy Fuel spray (HVOF), and Vacuum Plasma Spray (VPS). While widely adopted in the industry, some uncertainties remain as to the specific microstructural attributes which are influenced by the processing routes and their implications on durability. This paper seeks to elucidate these subtleties between bond coat deposition processing routes through an integrated study of processing to connect to furnace cycle durability on a single bond coat chemistry of NiCoCrAlYHfSi. A standard porous APS TBC top coating based on yttria stabilized zirconia (7YSZ) was consistently applied on these distinct bond coats and tested for durability in cyclic furnace testing at 1100 °C. The results point to substantial differences in durability which are not readily explained only by the variances in coating roughness. Detailed assessment of deposited bond coat properties (modulus, thermal expansion, chemistry) provided some explanation relative to durability. The results suggest a complex interplay among roughness, compliance, aluminum diffusion pathway, and thermal expansion mismatch. Photo-stimulated luminescence piezospectroscopy (PLPS) provided additional insights enabling a comprehensive assessment of processing-performance linkages.

As alternative lubricant anti-wear additives are sought to reduce friction and improve overall fuel economy, it is important that these additives are also compatible with current emissions control catalysts. In the present work, a second-generation oil-miscible phosphorous-containing ionic liquid (IL), is evaluated for its impact on Pd-based three-way catalyst (TWC) reactivity and benchmarked against the industry standard zinc dialkyl-dithio-phosphate (ZDDP). The TWCs are exposed to the lubricant additives in an engine bench under four different scenarios: base case with no additive (NA), ZDDP-only, IL-only, and IL + ZDDP. The engine-aged TWC samples, along with the as-received TWC, are characterized through various analytical techniques including catalyst reactivity evaluation in a bench-flow reactor. The temperature of 50% conversion (T50) for the ZDDP-aged TWC increases by 11, 21, and 36 °C for CO, C3H6, and C3H8, respectively, as compared with the no-additive case. Similarly, the T50 for IL-only and IL + ZDDP-aged TWCs also increase as compared with the no-additive case. Even though the water-gas-shift (WGS) reactivity is similar for all engine-aged samples, the IL-aged TWC had higher oxygen storage capacity than the ZDDP-aged TWC. EPMA analysis reveals penetration of phosphorus deep into the washcoat for all engine-aged TWCs. Results from XRD indicate the presence of CePO4 and AlPO4 on the washcoat of IL, ZDDP, and IL + ZDDP-aged TWC samples but not on the fresh and NA TWC samples. Additionally, ICP-OES results show a large amount of phosphorus in the washcoat of IL, ZDDP and IL + ZDDP-aged TWC samples and a lesser amount in NA TWC samples.

Three-way catalysts (TWC) coated within gasoline particulate filter (GPF) walls (TWC/GPF) were tested in a gasoline direct injection (GDI) engine to investigate the impact of engine oil-derived che...

The development of three-way catalysts with improved low temperature activity is essential for automotive catalysis. Here, we show that solution atomic layer deposition (SALD) of titania or zirconia promoters on alumina supports lowers the light-off temperatures of rhodium-based catalysts by 50–150 °C compared to a commercial benchmark three-way catalyst. X-ray diffraction, scanning transmission electron microscopy–electron energy loss spectroscopy, diffuse reflectance UV–visible spectroscopy and X-ray absorption near edge structure results indicate that titania incorporated by SALD at one monolayer loading is present primarily as atomically disperse 5-coordinate Ti4+ species. These species persist after exposure to steam and corrosive gases at temperatures up to 960 °C. Zirconia incorporated onto alumina by SALD is present as few-nanometre oxide particles and supports a three-way catalyst activity that is superior to that of Rh on either alumina or zirconia. Our results show that molecularly precise synthesis can lead to robust promotion of precious metal activity and provide a promising path towards reducing emissions from gasoline vehicles. Improving the performance of commercial three-way catalysts like rhodium on alumina is a major challenge considering the limited design space allowed for such systems. Now, solution atomic layer deposition is used to incorporate titania or zirconia promoters into this catalyst, leading to remarkable improvements in its overall performance.

Passive selective catalytic reduction (SCR) is a promising approach for the control of NOX emissions in lean burn gasoline exhausts. It requires ammonia (NH3) to be produced over a three-way catalyst (TWC) during periods of fuel-rich operation for the reduction of NOX during periods of fuel-lean operation. Previous research has shown the viability of this system but has not examined the effects of hydrothermal degradation. This work is focused on evaluating the effects of hydrothermal aging on the TWC in a passive SCR system. Two catalysts were studied: a Pd-TWC, and a NOX storage and reduction (NSR) TWC. Samples were aged at 920 °C for 100 h using a four-mode hydrothermal aging procedure. This causes the catalyst to be oxidized and reduced, as it would in a real system. The effects of aging were evaluated using simulated exhaust under both steady state and lean-rich cycling conditions. Hydrothermal aging caused significant changes in catalyst activity, leading to a decrease in low temperature conversion of carbon monoxide (CO) and propane (C3H8) on both catalysts, and degradation of oxygen storage and NOX storage components. However, the catalysts maintained their activity for NOX conversion and NH3 production, showing sufficient activity for the operation of a passive SCR with an optimum projected fuel consumption of 92–98% compared to stoichiometric operation.

To study the benefit of ~ 50-µm-thick air-plasma-sprayed (APS) ‘flash’ bond coatings, NiCoCrAlYHfSi high-velocity oxygen fuel (HVOF) bond coatings were deposited on alloy 247 disk substrates with APS yttria-stabilized zirconia topcoatings. Using 1-h cycles at 1100 °C in air with 10% H2O and HVOF-only bond coatings as a baseline, APS flash coatings extended the average coating lifetime by > 10% using NiCoCrAlYHfSi and > 70% using NiCoCrAlY powder. Coatings were characterized after 0, 100 and 300 cycles and after failure. Residual stress in the thermally grown alumina scale was mapped every 100 cycles using photo-stimulated luminescence piezospectroscopy. The flash coating created an interlocked metal–alumina layer that appeared to inhibit critical crack formation, and the underlying HVOF layer prevented further internal oxidation and appeared to supply the APS flash coating with Al. The addition of Hf and Y to the flash coating increased internal oxidation and accelerated Al consumption, thereby reducing the benefit of the flash coating.

Specimen deformation, oxide scale growth, and scale cracking were monitored for cyclic oxidation exposures at 1200 °C of three cast FeCrAlY(Hf) alloys and two oxide dispersion strengthened (ODS) FeCrAl alloys. Evolution of both the specimen geometry and surface deformation was quantified using 3D optical microscopy. The stress in the alumina scale was also measured using photo-stimulated luminescence piezospectroscopy. The goal was to assess the effect of stress generation and stress relaxation on scale spallation for FeCrAl materials with drastic differences in terms of high temperature strengths. After 1000, 1-h cycles, the cast alloys exhibited significant deformation with a convoluted oxide scale, leading for the two Hf-free FeCrAlY alloys to undergo crack formation and spallation. For the Hf-containing FeCrAlY, limited spallation was observed due to the localization of spallation at grain boundaries, the large grain structure, and the beneficial effect of Hf on scale adhesion. In contrast, limited deformation was measured for the ODS FeCrAl alloys, with minimal cracking and scale spallation for alloy PM2000 after 1000 h. A higher spallation rate was observed for ODS MA956, which was attributed to a high defect concentration in the alumina scale that formed. The mechanisms leading to spallation during cyclic oxidation for the cast and ODS FeCrAlY alloys are described.

Oxidation resistant overlay coatings protect the underlying superalloy component in industrial gas turbines from oxidation attack. Rate of depletion of the Al-rich β-phase in the bond coat governs the lifetime of these coatings. The applicability of a computational method in accelerating the development of corrosion resistant coatings and significantly reducing the extensive experimental effort to predict coating lifetimes and microstructural changes in three-coated Ni-based superalloys for real operational durations (20–40 kh) was undertaken in the present study. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and electron microprobe analysis (EPMA) were employed to characterize MCrAlY-coated superalloy substrates (1483, 247 and X4) after exposure at 900 °C in air + 10% H2O for up to 20,000 h. The model predicted the longest coating lifetime for the coating on X4 substrate. Precipitation of γ′ in the coatings was correctly predicted for all three coating systems. Additionally, the model was able to predict the formation of topologically close packed (TCP)-phases in the investigated coating systems.

The addition of an air plasma sprayed (APS) “flash” layer on top of a high velocity oxygen fuel (HVOF) bond coating has been shown to extend the lifetime of thermal barrier coatings. A series of furnace cycle tests (FCTs) has been conducted at 1100 °C in air + 10% H2O to study the benefit of flash coatings on rod and disk alloy 247 specimens and provide a better mechanistic understanding of their benefit. Flash coatings of NiCoCrAlY and NiCoCrAlYHfSi both improved the FCT lifetime of rod specimens tested in 100-h cycles and disk specimens tested in 1-h cycles. In 1-h cycles, the NiCoCrAlY flash coating significantly outperformed an HVOF-only NiCoCrAlYHfSi bond coating and a NiCoCrAlYHfSi flash coating. Both flash coatings increased the bond coating roughness compared to HVOF. During exposure, the flash layer formed an intermixed alumina-metal layer that appeared to inhibit crack formation. Using a time series of observations, the lower Y + Hf content in the Y-only flash coating appeared to reduce Al consumption. The HVOF layer acted as a source of Al for the adjacent mixed zone. A second series of specimens included a fully APS bond coating where oxide had penetrated through the entire coating to the substrate after only 100, 1-h cycles and lifetime was similar to an HVOF-only bond coating. The inner HVOF layer with the outer APS flash coating prevented this complete penetration from occurring.

Exhaust gas recirculation (EGR) cooler fouling occurs when particulate matter (PM) and hydrocarbons (HC) in diesel exhaust form a deposit on the walls of the EGR cooler through thermophoresis and condensation. To better understand the mechanisms controlling deposit formation and removal and how operating conditions can affect cooler performance, 20 identical tube-in-shell EGR coolers with sinusoidal fins were fouled using a 5-factor, 3-level experimental design. The deposit thickness was measured using two methods: (1) epoxy-mounting and polishing cooler cross-sections and comparing deposit thicknesses on the primary (outer tube) to the secondary (fins) heat transfer surfaces, and (2) milling tube sections such that the surface of a fin could be observed and measuring the deposit thickness across the fin using a 3D profilometer. Near the cooler inlet, high inlet gas temperatures reduced deposit thickness by promoting mud-cracking and spallation. Near the middle of the cooler, the flow rate had the largest impact on the deposit thickness through the effect on residence time of the PM. The HC concentration along with flow rate had the largest effects near the cooler outlet where the lower temperatures allows for more HC condensation. These insights into how engine operating conditions influence the development of fouling layers in EGR coolers learned through this study will aid in the development of more fouling resistant coolers in the future.

A coupled thermalhydraulic-neutronic extended criterion developed in order to assess the conditions of static instability of the sodium flow in a SFR core during the beginning of an unprotected loss of flow (ULOF) is presented in the first part of this paper. This extended criterion takes into account the evolution of the pressure drop in a sub-assembly (SA) as well as the evolution of its power when the reactor is affected by a flow rate (or power) perturbation by starting from a steady-state. The considered steady states are typical of quasi-steady states reached by a SFR during a ULOF. The temporal evolution of the flow and the temporal evolution of the power can be represented by a system of two differential equations whose linear stability analysis has enabled to define the aforementioned extended criterion. Then, in the second part of the paper, a verification of this extended criterion is performed by simulating the behavior of a GEN IV SFR of 1500 MWth. Four various steady states of the reactor have been investigated with a simulation tool devoted to unprotected loss of flow simulations (MACARENa). First simulations have enabled to calculate the various physical parameters needed to check the extended criterion. Perturbations have been applied to these four states. The extended criterion, proposed in this paper, has predicted flow stabilization for 3 states whereas it has predicted a flow excursion (sudden flow rate decrease leading to SA dry-out) for the last state. In this latter case, the classical Ledinegg criterion, which relies only on pressure drop evolution at constant power, has predicted a stable configuration. Then, the extended criterion predictions have been verified with MACARENa simulations, by slightly and temporary reducing the driving pressure head of the flow rate in the studied SA from each of the four initial states. For stable states, when setting again the pressure head of the flow to the value of the initial state, the initial flow rate is recovered. For the last initial state (predicted as unstable by the extended criterion), after a convergence period carried-out by imposing the SA steady flow rate, the solving of the transient momentum equation have shown that a flow excursion occurs in the MACARENa simulation as expected from the extended criterion. Consequently, the extended criterion proposed in this paper has been verified and could enable to define stable and unstable domain of couple flow rate/power in order to design future cores.

The effects of Ti and B additions to a vacuum plasma sprayed (VPS) NiCoCrAlYHfSi bond coating on thermal barrier coating (TBC) performance were studied at 1100 °C and 900 °C and compared to high-velocity oxy-fuel (HVOF) bond coatings. Using alloy 247 substrates and air plasma sprayed Y2O3-stabilized ZrO2 top coatings, additions of B or Ti + B did not improve the average TBC lifetime in 1-h cycles at 1100 °C in air with 10% H2O. The addition of Ti resulted in a decrease in lifetime. Photo-stimulated luminescence spectroscopy was used to map residual stresses in the thermally-grown Al2O3 scale. At 900 °C, closer to a typical land based turbine operating bond coating temperature, specimens were examined after ten 500-h cycles in laboratory air and air with 10%H2O to study the effect of H2O. The addition of water vapor had little effect on the measured parabolic rate constants at 900 °C and a comparison of the oxide microstructures in both environments is reported.

Pd-functionalized chabazite (Pd/SSZ-13) was evaluated for passive NOx adsorption (PNA) using low temperature combustion with diesel (LTC-D) reaction feed of the “United States Driving Research and Innovation for Vehicle efficiency and Energy sustainability” (U.S.DRIVE) protocol. Notably as per the protocol conditions, 12 % O2 + 6 % CO2 + 6 % H2O was flown in all cases. NO-uptake studies in the presence of the LTC-D feed showed a systematic decline with (NO:Pd)molar changing from 0.5 to 0.4 after 10 trials. Control experiments showed more pronounced decline for NO + CO case, with appreciable intial (NO:Pd)molar value of 0.4, yet comparable-to-the-LTC-D-feed decline after 8 trials. CO-induced particle formation and larger extent of particle sintering was also evident from TEM analysis. Other controls did not exhibit trial-dependent deactivation as (NO:Pd)molar values were similar between trials, at 0.3, 0.2, 0.5 and 0.2 for NO, NO+H2, NO + unsaturated hydrocarbon (C2H4, C3H6) and NO + saturated HC (C3H8, C10H22) feeds respectively. In addition to these quantitative differences, desorption behaviors are qualitatively different. While only one major desorption event was observed for the full LTC-D feed, NO + CO and NO + unsaturated HC-controls, desorption occured in two distinct stages for NO, NO + saturated HCs and initial-NO+H2 trials. This arises due to inherent differences in Pd sites while exposed to these chemically distinct feeds. The presence of CO and unsaturated HCs in the feed resulted in almost complete elimination of lower, sub-200 °C desorption peak. The higher temperature desorption peaks, at > 300 °C is associated with NO strongly bound to ionic Pd sites and are prevalent under reducing conditions. Using DRIFTS also, three complexes leading to PNA are assigned, [O N–Pd2+(OH)–Z], [O N–Pd2+(Z2)] and [O N–Pd2+(H2O)y–Z] with the latter being clearly observed upon water exposure. Pd/SSZ-13 showed higher hydrocarbon trapping than the SSZ-13 counterpart.

International audience; Hydrothermally stable diesel oxidation catalysts (DOCs) with improved low-temperature activity are desired for the abatement of emissions from diesel vehicles. Herein, novel palladium(Pd)/SiO2(core)@Zr(shell) structured DOCs were developed. SiO2 was completely covered by an 8.4 nm thickness Zr-based shell using a hard template method. The SiO2@Zr support was decorated by Pd and evaluated under a simulated diesel exhaust stream. Degreened 1 wt% Pd/SiO2@Zr achieved 90% CO and total hydrocarbon conversion at 178 and 372 °C, respectively (feed: 6% CO2, 12% O2, 6% H2O, 400 ppm H2, 2000 ppm CO, 100 ppm NO, 1667 ppm C2H4, 1000 ppm C3H6, 333 ppm C3H8; HCs in C1 basis and GHSV = 113,000 h−1). After hydrothermal aging, only a minor deactivation was observed, while the surface area of 1 wt% Pd/SiO2@Zr was as high as 104 m2/g. The hydrothermal stability of 1 wt% Pd/SiO2@Zr was attributed to the poor crystallinity of SiO2@Zr, possibly due to the formation of Si-O-Zr bonds. This work highlights the promising potential of utilizing durable Pd/SiO2@Zr catalysts for diesel oxidation applications

Increasing peak cylinder pressures and operating temperatures of turbo-charged internal combustion engines (ICEs) engines present new challenges for existing materials employed in engine exhaust valves. Oxidation induced degradation of current Ni based alloys for these components will be a life-limiting mechanism while strict cost margins in the automotive transportation industry further limit the choice of suitable candidate materials. Metallic diffusion aluminide coatings can provide a cost-effective way to improve the oxidation resistance of underlying materials. In this study, the high temperature oxidation behavior of diffusion nickel aluminide coatings on two Ni based alloys (commercially available alloy 31V and a developmental alloy) during cyclic oxidation behavior in air+10% H2O at 900 °C was investigated. A complete depletion of the beneficial Al-rich β-(NiFe)Al phase was observed in the coating on alloy 31V while a significant fraction of this phase was retained in the coating on the second alloy. A coupled thermodynamic-kinetic model showed that the disappearance of the Al-rich phase in the coating on 31V was mainly due to the combined effect of steeper chemical potential gradients of Al and Ti between the coating and the substrate and their faster diffusivities compared to the coated developmental alloy. A higher content of Fe was shown to support the retention of β-(NiFe)Al phase in the coating on the developmental alloy while the presence of Ti in the alloy was shown to be detrimental for long-term coating performance.

In the present study, two industry primary and secondary zinc dialkyldithiophosphate standards, ZDDP1 and ZDDP2, respectively, are evaluated for their impact on the performance of Pd-based three-way catalyst and bench-marked against two mixed lubricant additives formed from either ZDDP1 or ZDDP2 with a second-generation oil-miscible phosphoric-containing ionic liquid (IL). The three-way catalysts (TWCs) are exposed to the lubricant additives in an engine bench under four different scenarios: a base case with no additive (NA), ZDDP1, IL+ZDDP1, ZDDP2, and IL+ZDDP2. The engine-aged TWC samples are characterized through a variety of analytical techniques, including evaluation of catalyst reactivity in a bench-flow reactor. With respect to the water–gas shift reaction and the oxygen storage capacity, the ZDDP2- and IL+ZDDP2-aged TWC samples are more degraded than the ZDDP1- and IL+ZDDP1-aged TWC samples. X-ray diffraction (XRD) patterns indicate that phosphorus in the form of CePO4 was found to be present in the washcoat of all TWC samples, with the highest amount found in the ZDDP2-aged TWC sample. The results obtained from XRD are further confirmed by those from inductively coupled plasma-optical emission spectroscopy (ICP-OES), which show that more phosphorus is detected in the washcoat of ZDDP2- and IL+ZDDP2-aged TWC samples than in the ZDDP1- and IL+ZDDP1-aged TWC samples.

The apparent fracture toughness of a porous cordierite ceramic was estimated using a large specimen whose geometry was inspired by the ASTM-C1421-standardized chevron-notch beam. Using the same combination of experiment and analysis used to develop the standardized chevron-notch test for small, monolithic ceramic bend bars, an apparent fracture toughness of 0.6 and 0.9 MPa√m were estimated for an unaged and aged cordierite diesel particulate filter structure, respectively. The effectiveness and simplicity of this adapted specimen geometry and test method lends itself to the evaluation of (macroscopic) apparent fracture toughness of an entire porous-ceramic, diesel particulate filter structure.

The high activity observed on Pd impregnated MnOx–CeO2 solid solution catalysts for low temperature CO oxidation is investigated through in situ extended X-ray absorption fine structure (EXAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments. The change in the Pd local structure on CeO2 and MnOx–CeO2 is studied to identify the role of oxidized Pd nanoparticles during CO oxidation. EXAFS analysis of the calcined samples confirms the formation of PdO structures on CeO2 and MnOx–CeO2 supports. The structural model applied to the Ce1−xPdxO2−δ interaction phase could not predict the second and third near-neighbor coordination shells of Pd. Sintering and re-dispersion of Pd is observed on CeO2 during H2 reduction and subsequent oxidation with air. During CO oxidation, PdO species are reduced by CO on CeO2, forming a mixture of Pdn+/Pd0 species. These reduced Pd particles can be re-oxidized and re-dispersed on the CeO2 surface forming larger PdO crystallites. In the case of Pd/MnOx–CeO2, Pdn+ species can be stabilized during the reaction and no obvious Pd0 formation could be detected. Due to the formation of similar PdO species after CO oxidation on both CeO2 and MnOx–CeO2 supports, the different low temperature CO oxidation activities can be associated with the oxygen storage properties and oxygen mobility of the support.

In order to assess the role of temperature on the lifetime of thermal barrier coatings (TBCs) and the development of residual stresses in Al2O3 scales grown under yttria-stabilized zirconia (YSZ) top coatings, two vacuum plasma sprayed (VPS) NiCoCrAlYHf bond coating (BC) compositions, with and without Si, were deposited on Hf-rich directionally-solidified (DS) 247 substrates and then coated with air plasma sprayed (APS) YSZ. Samples were thermally-cycled at temperatures ranging from 1075 to 1150 °C with 1-h cycles in air with 10% H2O. Photo-stimulated luminescence spectroscopy (PSLS) was used to map residual stresses in the Al2O3 scale at the YSZ/BC interface from the same region at regular cycling intervals. All samples exhibited similar stress distributions after 100 1-h cycles with the exception of the YHfSi BC cycled at 1150 °C which had a lower average compressive stress with more delaminations. This specimen also had the shortest TBC lifetime which shows that the PSLS measurements correlate well to interfacial damage accumulation in TBCs. The presence of Si had no effect on lifetime or residual stress but was found to reduce the amount of internal oxidation. The effect of sample curvature on the interfacial stress and TBC lifetime was also assessed by comparing TBC-coated rod specimens to flat buttons. Rod specimens failed much earlier than flat specimens and had lower Al2O3 residual stress.