Influence of rare earth promoters on the performance of Ni/Mg（Al）O catalysts for hydrogenation and steam reforming of toluene

CeO₂-, La₂O₃-, and ZrO₂-promoted Ni/Mg(Al)O catalysts synthesized by hydrotalcite-type precursors have been investigated with respect to catalytic activity and carbon formation in the hydrogenation and steam reforming of toluene as a model tar compound. X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area and H₂-temperature programmed reduction (TPR) were used to observe the characteristics of the prepared catalysts. The carbon formation and its amount on the used catalysts were examined by transmission electron microscope (TEM), scanning electron microscope (SEM) and thermogravimetric (TG). The trend of catalytic activity as derived from the experimental results followed the order: Ni-Ce>Ni-Las>Ni-Zr>Ni. The catalyst modified with CeO₂ exhibited the highest catalytic performance and had good carbon resistance in the hydrogenation and steam reforming of toluene. A toluene conversion of 96.8%, a CH₄ yield of 45.2% and a CO yield of 50.4% have been achieved. The addition of promoters led to better dispersion of nickel species and higher interaction nickel-support, which were favorable for increasing the catalytic activity and effectively preventing carbon formation.     

MoS2 coated with Al2O3 for Ni-MoS2/Al2O3 composite coatings by pulse electrodeposition

The MoS₂ powders were coated with Al₂O₃ (5 wt.%) through controlling hydrolysis of Al (NO₃)₃·9H₂O. MoS₂ powder coated with Al₂O₃ was written as MoS₂/Al₂O₃ hereinafter. MoS₂/Al₂O₃ powders were put into Ni plating electrolyte bath. Cetyltrimethylammonium bromide (CTAB) — the surfactant was also put into the bath. The experiment proves that MoS₂/Al₂O₃ particles were absorbed onto the Ni plate. The amount of MoS₂/Al₂O₃ deposited on Ni plate rises with the increasing concentration of MoS₂/Al₂O₃ in the bath. The microhardness, micro-surface, phase and the tribological property of the MoS₂/Al₂O₃ multi-plating coating were measured and analyzed. The performances of microhardness and wear resistance of the Ni-MoS₂/Al₂O₃ composite are better than those of Ni-MoS₂ composite.     

Effect of the suspension composition on the microstructural properties of high velocity suspension flame sprayed (HVSFS) Al2O3 coatings

Seven different Al₂O₃-based suspensions were prepared by dispersing two nano-sized Al₂O₃ powders (having analogous size distribution and chemical composition but different surface chemistry), one micron-sized powder and their mixtures in a water + isopropanol solution. High velocity suspension flame sprayed (HVSFS) coatings were deposited using these suspensions as feedstock and adopting two different sets of spray parameters.The characteristics of the suspension, particularly its agglomeration behaviour, have a significant influence on the coating deposition mechanism and, hence, on its properties (microstructure, hardness, elastic modulus). Dense and very smooth (Ra ~ 1.3 μm) coatings, consisting of well-flattened lamellae having a homogeneous size distribution, are obtained when micron-sized (~ 1-2 μm) powders with low tendency to agglomeration are employed. Spray parameters favouring the break-up of the few agglomerates present in the suspension enhance the deposition efficiency (up to > 50%), as no particle or agglomerate larger than ~ 2.5 μm can be fully melted. Nano-sized powders, by contrast, generally form stronger agglomerates, which cannot be significantly disrupted by adjusting the spray parameters. If the chosen nanopowder forms small agglomerates (up to a few microns), the deposition efficiency is satisfactory and the coating porosity is limited, although the lamellae generally have a wider size distribution, so that roughness is somewhat higher. If the nanopowder forms large agglomerates (on account of its surface chemistry), poor deposition efficiencies and porous layers are obtained.Although suspensions containing the pure micron-sized powder produce the densest coatings, the highest deposition efficiency (~ 70%) is obtained by suitable mixtures of micron- and nano-sized powders, on account of synergistic effects.     

Morphology and preferred orientation of Y2O3 film prepared by high-speed laser CVD

Yttria (Y₂O₃) films were prepared at high deposition rates of up to 83 nm/s (300 μm/h) by laser chemical vapor deposition (LCVD) using an Y(dpm)₃ precursor. The effects of deposition conditions, mainly total gas pressure and laser power, on morphology, deposition rate and preferred orientation were studied. Plasma was produced around the substrate over a critical laser power resulting in significant increases in deposition temperature and deposition rate. The high deposition rate (300 μm/h) by LCVD was about 100 to 1000 times as high as those by conventional CVD. The morphology of Y₂O₃ films changed from faceted and columnar structures with high (400) orientation to a columnar structure with high (440) orientation, and finally to a cone-like structure with moderate (440) orientation with increasing total gas pressure (P_tot).     

Failure of physical vapor deposition/plasma-sprayed thermal barrier coatings during thermal cycling

ZrO₂-7 wt.% Y₂O₃ plasma-sprayed (PS) coatings were applied on high-temperature Ni-based alloys precoated by physical vapor deposition with a thin, dense, stabilized zirconia coating (PVD bond coat). The PS coatings were applied by atmospheric plasma spraying (APS) and inert gas plasma spraying (IPS) at 2 bar for different substrate temperatures. The thermal barrier coatings (TBCs) were tested by furnace isothermal cycling and flame thermal cycling at maximum temperatures between 1000 and 1150 °C. The temperature gradients within the duplex PVD/PS thermal barrier coatings during the thermal cycling process were modeled using an unsteady heat transfer program. This modeling enables calculation of the transient thermal strains and stresses, which contributes to a better understanding of the failure mechanisms of the TBC during thermal cycling. The adherence and failure modes of these coating systems were experimentally studied during the high-temperature testing. The TBC failure mechanism during thermal cycling is discussed in light of coating transient stresses and substrate oxidation.     

In-situ TiB2 and Al2O3 formation by DC plasma spraying

In-situ plasma spraying (IPS) is a promising process to fabricate composite coatings with in-situ formed thermodynamically stable phases. In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). It has been observed that, during the coating process, TiB₂ and Al₂O₃ are in-situ formed through the reaction between starting powders and finely dispersed in hypereutectic Al-Si matrix alloy. Also, obtained results demonstrate that in-situ reaction intensity strongly depends on spray conditions.     

Influence of ZnO content and annealing temperature on the dielectric properties of ZnO/Al2O3 composite coatings

ZnO/Al₂O₃ coatings were prepared by atmospheric plasma spraying (APS) using ZnO powders and Al₂O₃ powders as starting materials. The dielectric properties of these coatings were discussed. Both the real part of permittivity and the energy loss increase greatly with increasing ZnO content over the frequency range 8.2-12.4 GHz, which can be ascribed to orientation polarization and relaxation polarization due to a higher ZnO content. The frequency-dependent maximum of the loss tangent is found to obey Debye theory. In addition, annealing temperature which leads to the change of ZnO content also plays an important role in the dielectric performance.     

Effect of catalyst calcination temperature on the synthesis of MWCNT-alumina hybrid compound using methane decomposition method

This work focuses on synthesis of MWCNT-alumina hybrid compound via methane decomposition process using Ni-Al₂O₃ catalyst. The catalysts prepared through in situ process by using nickel salt and aluminium powder which are then calcined at three different calcination temperatures (700 °C, 900 °C and 1100 °C). The catalyst calcined at 900 °C followed by methane decomposition process successfully yielded MWCNT-alumina hybrid compound. No trace of CNT was detected for catalyst calcined at 700 °C and 1100 °C. The scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) micrograph confirmed the formation of MWCNT with homogenous dispersion on alumina particles.     

Characterization of MOCVD-grown non-stoichiometric SiNx

The surface morphologies and X-ray photoelectron spectra of MOCVD-grown SiN_x were investigated. Highly Si-rich SiN_x nanoislands not fully covering the sapphire surface were observed for SiN_x deposition at low temperature (545 °C) with NH₃/SiH₄ flow rate of 2500/40 sccm. The surface roughness decreased from 0.91 nm to 0.23 nm with the reduction of SiH₄ flow rate from 40 sccm to 3 sccm. The reduction of the SiH₄ flow rate did not cause a linear decrease of Si/N ratio, which indicated that the SiH₄ supply was saturated when the NH₃ supply was 2500 sccm and deposition temperature was fixed at 545 °C. Relatively “thick” SiN_x layers with stoichiometry close to 1 were formed for SiN_x deposition at high temperature due to high decomposition rate of ammonia and high reaction rate between silane and ammonia. The SiN_x layers almost fully covered the sapphire surface and showed surface structures of both nanoislands and nanoholes. By employing the same NH₃/SiH₄ flow rate of 2500/40 sccm the surface roughness of SiN_x layers decreased from 0.91 nm to 0.17 nm with the increase of deposition temperature from 545 °C to 1035 °C. Saturated pre-nitridation would likely cause surface roughening.     

Development and characterization of single wire-arc-plasma sprayed coatings of nickel on carbon blocks and alumina tube substrates

A single wire-arc-plasma spray torch has been used to develop metal coatings on carbon and alumina substrates under argon atmosphere for various applications. Nickel coatings of around 1 mm thickness have been deposited on selected area (60 mm × 200 mm on each side) of large size carbon blocks by intermittent arc spraying and cooling to reduce thermal stresses and possibility of coating de-lamination from the base substrate. The same process is also used for depositing about 3 mm thick nickel metal coatings (8 mm dia. × 40 mm long) on alumina tubes for developing electrical feed throughs. The nickel coated alumina tubes were tested for the vacuum compatibility of the coated material with the base tube. The coated assemblies could withstand vacuum of the order of 1 × 10^− 6 Torr and the leak rate was found to be less than 1 × 10^− 9 Std. cc/s for Helium gas, indicating excellent bonding of the coated metal with alumina ceramics and no connected open porosity in the coatings. X-ray diffraction studies were conducted for identifying the phases and the optical microscope with image analysis technique was used for studying the microstructure and porosity in the coatings.     

Selective catalytic reduction of NO with propene over Au/CeO2/Al2O3 catalysts

Selective catalytic reduction of NO by propene under an oxygen-rich atmosphere has been investigated over Au/ CeO₂, Au/CeO₂/Al₂O₃ and Au/Al₂O₃ catalysts prepared by deposition-precipitation. The results demonstrated that Au/16%CeO₂/Al₂O₃ had good low-temperature activity, selectivity towards N₂ and stability, which is superior to that of Pt/Al₂O₃. It was also found that adding 2% water vapour to the feed stream enhanced the NO conversions at low temperatures while the presence of 20 ppm SO₂ increased NO conversions at higher temperatures. It is particularly interesting that under the simultaneous presence of 2% water vapour and 20 ppm SO₂, the NO conversions to N₂ were significantly increased and the temperature window was widened significantly. The catalysts were characterized by Xray diffraction (XRD), high resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy (HRTEM-EDX) and temperatureprogrammed reduction (H2-TPR) techniques. Both XRD and HRTEM revealed that CeO₂ was highly dispersed on the alumina support, and HRTEM combined with EDX showed that gold particles were preferentially deposited on those highly dispersed CeO₂ particles. The gold deposition made CeO₂ more reducible and interaction between gold and those highly dispersed CeO₂ particles became stronger than that with the bulk CeO₂, and this interaction is probably responsible for the superior catalytic performance of the Au/CeO₂/Al₂O₃.     

包覆型镍基催化剂DRM反应研究

Ni纳米颗粒是甲烷干重整反应(DRM)中的高效催化剂。然而,当应用于实际条件下的DRM反应时,克服由于烧结和积碳引起的催化剂失活,提高催化剂耐久性是其面临的巨大挑战。通过原子层沉积(ALD)技术制备了不连续包覆的FeOx-Ni复合纳米催化结构,显著改善了催化活性,并有效抑制了DRM反应中的碳沉积。通过精确调控Ni纳米颗粒上FeOx包覆层的密度可以实现最佳的催化性能,在650℃下,CH4的转化率由52.21%提高到64.27%。一方面,不连续的包覆结构将Ni表面分隔开,以防止形成碳纳米管钝化催化剂。另一方面,FeOx提供了部分甲烷分解的活性位点,这有利于催化剂活性的提升。同时,FeOx的添加,增强了CO2的吸附和活化,减少了碳中间体的形成。Fe含量为0.1%(质量分数)的FeOx/Ni/Al2O3在650℃反应72 h后活性(CH4转化率)仅降低7%,耐久性良好。     

In-process exothermic reaction in high-velocity oxyfuel and plasma spraying with SiO<Subscript>2</Subscript>/Ni/Al-Si-Mg composite powder

Reactive thermal spraying, in which thermodynamically stable compounds are formed by expected inprocess reactions, has attracted considerable attention as a result of the wide availability of in situ composite coatings. Such in-process reactions occur differently in high-velocity oxyfuel (HVOF) and plasma spraying because of differences in the flame temperature and speed. In the current study, a composite powder of SiO₂/Ni/Al-Si-Mg was deposited onto an aluminum substrate to fabricate in situ composite coatings by both spraying methods. The coating hardness sprayed with Al-Si-Mg core powder increases with silicon and magnesium content, whereas the coatings by HVOF spraying show higher hardness than those by plasma spraying. In the present reactive spraying, the exothermic reaction of SiO₂ with molten Al-Si-Mg alloy leads to composite materials of MgAl₂O₄, Mg₂Si, and Al-Si matrix. Moreover, a rapid formation of aluminide (NiAl₃), which is introduced by an exothermic reaction of plated nickel with Al-Si-Mg core powder, enhances the reduction of SiO₂, especially in HVOF spraying. A series of in-process reactions proceed mainly during splat layering on a substrate instead of during droplet flight even in plasma spraying. Plasma-sprayed composite coatings become much harder because of the great progress of in-process reactions.     

Enhanced tribological properties of PECVD DLC coated thermally sprayed coatings

This research investigates the enhancement of the tribological properties of various thermally-sprayed coatings (APS Ni-50Cr, APS Al₂O₃-13%TiO₂ and HVOF WC-17Co) on steel substrate, achieved through the deposition of a thin DLC-based film. Higher adhesive strength between thin films and thermally-sprayed coatings compared to the simple thin film/carbon steel system was found by scratch testing. Dry sliding ball-on-disk tests performed under lower contact pressure conditions (5 N normal load, 6 mm diameter alumina ball) indicated a significant decrease in wear rates and friction coefficients of thermally-sprayed coatings when the thin DLC-based film is employed; little differences exist between the tribological behaviour of the various thin film/thermal spray coating systems and that of DLC-based film on carbon steel. Under higher contact pressure conditions (10 N normal load, 3 mm diameter alumina ball), the thin film/WC-Co system exhibited the best wear performance. These results indicate the superior tribological performance of DLC/thermal spray coating systems, especially under severe contact conditions.     

The yttrium effect on the corrosion resistance of CO2-laser processed MCrAlY coatings

To improve the corrosion resistance and to study the effect of yttrium in the behavior of coatings produced by thermal spraying MCrAlY (M=Ni, Co) powders, CO₂ laser processing was conducted. Three methods were used: (1) a combination of gas flame and plasma spraying in air followed by laser glazing in argon, (2) low-pressure plasma spraying (LPPS) and laser glazing in argon, and (3) LPPS and laser-gas (O₂) alloying. Laser glazing in argon of the MCrAlY coatings sprayed in air promoted formation of weakly adherent agglomerates of Al–Y oxides and an alumina-chromia solid solution. Glazing in argon atmosphere of LPPS CoNiCrAlY and NiCrAlY coatings caused the formation of nickel aluminides besides the formation of Y–Al compounds. Gas (O₂)-alloying of these coatings produces continuous and adherent (yttrium-containing) alumina and chromia layers. The effects of yttrium on the characteristics of the oxides formed in the coatings during laser glazing, laser-gas alloying, and high-temperature oxidation is discussed. This work also investigated the oxidation resistance of the laser-processed MCrAlY coatings in air and in the presence of 85 mol/o V₂O₅–Na₂SO₄ fused salt at 900°C.     

Effects of plasma treatment on bioactivity of TiO2 coatings

In this work, nano-TiO₂ powders were deposited on titanium alloy substrates by atmospheric plasma spraying, followed by plasma immersion ion implantation (PIII) using hydrogen, oxygen and ammonia gases. The bioactivities of PIII-treated TiO₂ coatings were evaluated by the formation of apatite on their surface after soaked in simulated body fluids (SBF) for a period of time. As-sprayed TiO₂ coating is composed of rutile, anatase and TiO_2−x (most of them is Ti₃O₅). After immersion in SBF for two weeks, the hydrogen PIII-treated TiO₂ coating can induce bone-like apatite formation on its surface but apatite cannot be formed on the surface of as-sprayed and oxygen, ammonia PIII-treated TiO₂ coatings. The results obtained indicated that a hydrogenated surface plays a very important role to induce bioactivity of TiO₂ coatings.     

La2O3-modified YSZ coatings: High-temperature stability and improved thermal barrier properties

Lanthana precursor was coated on yttria-stabilized-zirconia (YSZ) powders by wet chemical infiltration, and was introduced to the crystalline structure and grain boundaries of YSZ after plasma spraying of thermal barrier coatings (TBCs). The microstructural stability and thermal barrier properties of this new kind of TBCs were studied under different annealing conditions. It demonstrates that the La₂O₃ surface coating restrains grain growth of YSZ during both deposition and post-annealing processes, compared to a TBC obtained from commercially available unmodified YSZ powders. According to the composition analysis, lanthana partially dissolved in the zirconia matrix after heat treatment. The thermal diffusivity of YSZ coating significantly decreased after lanthana modification, typically from 0.354 mm² s^− 1 for an unmodified sample to 0.243 mm² s^− 1, reflecting a decrease of 31%. Even after annealed at 1200 °C for 50 h, the thermal diffusivity of modified coatings still shows a reduction of 25% than unmodified samples.     

Artificial neural networks implementation in plasma spray process: Prediction of power parameters and in-flight particle characteristics vs. desired coating structural attributes

Artificial neural networks (ANN) were implemented to predict atmospheric plasma spraying (APS) process parameters to manufacture a coating with the desired structural characteristics.The specific case of predicting power parameters to manufacture grey alumina (Al₂O₃-TiO₂, 13% by wt.) coatings was considered. Deposition yield and porosity were the coating structural characteristics.After having defined, trained and tested ANN, power parameters (arc current intensity, total plasma gas flow, hydrogen content) and resulting in-flight particle characteristics (average temperature and velocity) were computed considering several scenarios. The first one deals at the same time with the two structural characteristics as constraints. The others one deals with one structural characteristic as constraint while the other is fixed at a constant value.     

Properties of TiO2 support and the performance of Au/TiO2 Catalyst for CO oxidation reaction

Gold catalysts were prepared on TiO₂ supports of different phase structures (i.e., anatase, rutile and biphasic), TiO₂ crystal size (i.e., 9–23 nm), surface and textural properties (i.e., hydration and surface area). The CO oxidation on the gold catalysts was carried out in an operando-DRIFTS set-up equipped with DRIFTS reactor cell connected on-line to CO gas analyser and gas chromatograph enabling real time monitoring of surface reaction and simultaneous reaction rate measurements. Gold catalysts supported on pure anatase TiO₂ were more resistant to sintering compared to catalysts supported on rutile and bi-phasic TiO₂. Besides catalyst sintering, deposition of surface carbonates is an important cause of catalyst deactivation. The best gold catalyst was prepared on 13 nm anatase TiO₂. It displays both increased activity and stability for CO oxidation reaction at room temperature. Surface and textural properties of TiO₂ also play a role on the performance of the Au/TiO₂ catalyst.     

Preparation and properties of K2NiF4-type perovskite oxides La2NiO4 catalysts for steam reforming of ethanol

The performance of La₂NiO₄ perovskite catalysts, prepared using a citric acid complexation method, for the steam reforming of ethanol was studied. The catalysts were characterized by X-ray diffractometry (XRD), specific surface area measurements (BET), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The experimental results show that the calcination temperature and the amount of citric acid (CA) have a significant influence on the characteristics of the catalysts and their catalytic activity. Among the catalysts tested, the La₂NiO₄ catalyst calcined at 700 °C with n(La):n(Ni):n(CA) of 2:1:3 exhibits the best activity and excellent stability as well as very low coke formation.