Comparative study on the corrosion and wear behavior of plasma-sprayed vs. high velocity oxygen fuel-sprayed Al8Si20BN ceramic coatings

Corrosion and wear are common problems encountered in the oil and gas industry. These entail the gradual destruction of materials by mechanical action on the opposite surface, and the chemical and/or electrochemical reaction with their environment. In this research, Al8Si20BN ceramic powder with specific properties against corrosion and wear was selected, and it was sprayed with high velocity oxygen fuel (HVOF) and plasma spray methods onto carbon steel substrates. The coatings were characterized with respect to phase composition, microstructure, microhardness and adhesion strength. Their wear behavior was inspected by applying 5, 10, 15 and 20?N loads by pin-on-disc machine, after which the results of both methods were compared. According to the results, the HVOF-coated models were more durable than the plasma-coated models under different loads in the same condition. In addition, the corrosion deterioration of the coated specimens in both brine (3.5% NaCl) and fossil oil were tested for one month (30 days). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) assessment in 3.5% NaCl solution indicated that the HVOF-sprayed specimens had better corrosion protection than the plasma-sprayed specimens. Generally, the HVOF technique facilitated more durable coats with greater corrosion and tribological resistance compared to the plasma coating technique.     

Synergistic effect of CeO2 and Al2O3 nanoparticle dispersion on the oxidation behavior of MCrAlY coatings deposited by HVOF

In this study, the as-received and nano-scaled oxide dispersion strengthened (ODS) MCrAlY coatings were deposited using high-velocity oxy-fuel (HVOF) spraying process. The high-energy planetary ball-milling process was utilized to prepare CeO₂ and Al₂O₃ nanoparticles. ODS-NiCoCrAlY feedstock powders were also developed using the ball-milling process. The various formulations of Al₂O₃ and CeO₂ nanoparticles (0.5 and 1.0 wt%) were chosen to apply different types of ODS-NiCoCrAlY coatings. The microstructure of the as-received and ODS coatings were evaluated by field emission scanning electron microscope (FESEM) as well as the commercial and ODS powders. Furthermore, the microhardness of different compositions of ODS coatings was accordingly investigated and the obtained results were compared with as-received coating. On account of the measurement of oxidation kinetics, the freestanding as-received and ODS coatings were exposed to air at 1000 °C up to 500 h and the thickness growth rate of the α-Al₂O₃ oxide layer was simultaneously examined. The results exemplified that NiCoCrAlY+1.0 wt% nano-CeO₂+0.5 wt% nano-Al₂O₃ coating had a better oxidation resistance and lower oxide scale growth rate under the synergistic effects of both CeO₂ and Al₂O₃ nanoparticles.     

Microstructure and tribological behavior of Ti3C2Tx MXene reinforced chemically bonded silicate ceramic coatings

MXenes – In recent decades, great attention has been paid to the fast-growing two-dimensional (2D) transition metal carbides and nitrides, in terms of their prominent mechanical and electrical properties. The tribological essence of MXene has not yet been entirely investigated, although researches on MXene were conducted in all aspects of its applications. Hence, a newly compound 2D MXene (Ti₃C₂T_x) is exploited to reinforce the wear resistance of the chemically bonded silicate ceramic coatings, which are utilized to protect component surfaces under severe conditions. The structural features, hardness, and tribological behaviors of the targeted coatings are investigated and analyzed. Results show that the micro-hardness of the coatings increases to 156.9 HV_0.5 when added 1.2 wt% MXene. The increment of microhardness extraordinarily reaches 33.3%, compared with the original. The coating with 1.2 wt% MXene also indicates a 31.6% decrement of the coefficient of friction (COF) and a 73% reduction of the wear rate respectively. Furthermore, fatigue is found to be the main reason of the wear mechanism, through exploring the surface morphologies of wear traces and counterpart balls.     

A comparative investigation of the tribological behavior and scratch response of polyester powder coatings filled with different solid lubricants

Employing coatings is one of the most effective methods to reduce friction and protect contacting surfaces from wear. The deposition of protective coatings from thermosetting polymer powders has witnessed a rapid growth as an ecological, economic and energy efficient technology. During the last few decades, many new deposition techniques have been developed, and more and more tribological coatings have been made available. In this context, our present investigation tried, firstly to analyze the friction and wear behavior of electrostatically sprayed polyester powder coatings deposited on an aluminum substrate and secondly to focus on the response of these thermosetting coatings to micromechanical deformation under scratch test loading. The effect of graphite and hexagonal boron nitride (hBN) solid lubricant fillers on the friction and wear behavior of polyester composite coatings was evaluated using a reciprocating tribometer under dry friction condition. The experimental findings show that the additions of graphite or hBN are effective in enhancing the wear life of polyester powder coatings. Meanwhile, under the same sliding conditions, the wear results revealed that the polyester coating filled with only 10 wt.% of graphite has a higher anti-wear ability compared to the polyester coating filled with the same weight fraction of hBN. Thus, the two reinforcing polyester matrix fillers play an important role in reducing the plastic deformation of the coatings and enhance the formation of thick third body between the sliding parts as the fraction of solid lubricant increases from 0 wt.% to 10 wt.%. From the scratch analyses, we deduced that coatings scratch behavior is severely affected by the kind and amount of fillers inside the polyester matrix. In fact, the best friction characteristic and scratch resistance are observed in the case of polyester coatings filled with very low amount of hBN (5 wt.%).     

A comparative study on the properties of Li2TiO3 powders and pebbles fabricated by different routes

Lithium titanate (Li₂TiO₃) is one of the promising candidate breeders for tritium self-sufficiency of deuterium(D)-tritium(T) fusion reaction. The differences in powder synthesis methods have a great impact on the properties of Li₂TiO₃ powders and the performance of Li₂TiO₃ ceramic pebbles. In this study, the Li₂TiO₃ powders were successfully synthesized by hydrothermal method and solid-state method, and then the pebbles were fabricated by the agar-based wet method. The mechanism of hydrothermal synthesis of Li₂TiO₃ powder was discussed. For the hydrothermal method, the Li₂TiO₃ powder with single phase can be obtained when the rate of Li/Ti = 2.4, and the powder presented two different morphology, which involved two reaction mechanisms, including in-situ phase transformation mechanism and dissolution-precipitation mechanism, the phase transformation from α-Li₂TiO₃ to β-Li₂TiO₃ accomplished at 400°C, which is lower than that of 750°C for solid-state method. Li₂TiO₃ pebbles prepared by the hydrothermal-wet method had a uniform pore distribution, an optimal grain size of 2.7 μm, a crushing load of 58.6 N, and relative density of 90.2%, respectively. In comparison, pebbles prepared by the solid-state-wet method also had better mechanical properties, which the crushing load and relative density were 53.9 N and 86.9% respectively under the optimal fabrication conditions.     

Wear behavior and microstructure of alumina-mullite-zirconia composites prepared by a novel method: Coating of zircon powder by aluminum alkoxide

The formation of the mullite phase is the main challenge in the preparation of alumina-mullite-zirconia (AMZ) composites. To overcome this limitation, a novel method based on the coating of zircon powder with aluminum alkoxide was proposed in this study. Reaction sintering of alumina and coated zircon was carried out at 1630 °C for 3 h. The microstructural, physical, mechanical, and tribological properties of samples were compared with the conventional AMZ composites prepared by common mixing of alumina and zircon. The microstructural analysis indicated the higher alumina phase of the sample prepared with the conventional method. On contrary, the samples prepared with the proposed method included higher percentages of mullite phase. In terms of mechanical properties, the conventional AMZ samples performed better. However, due to the beneficial effect of the mullite phase in tribological applications, the samples prepared with this new method show superior wear resistance. Especially, the samples prepared from 30 wt% aluminum alkoxide exhibited the best wear resistance. The delamination and adhesive wear mechanisms govern the wear process.     

A comparative study of duty cycle and argon / methane flow ratio effect on the tribological behavior of DLC coatings over nitrided Astaloy Mo-based steel

Surface properties of Astaloy Mo-based steel were enhanced by using DLC deposition. The specimens were formed by double-sided compaction and heated for 30 min at 1393 K, in the NH₃ atmosphere. Following this, the plasma nitriding process was applied to improve the adhesion of the DLC coating. Afterward, the DLC coating was performed by Pulsed DC PACVD. Surface characteristics were studied by changing the duty cycle and the Argon/Methane flow ratio. The reciprocating method was carried out to evaluate wear behavior. Field emission scanning electron microscopy equipped with EDS and Raman spectroscopy, hardness tester, nanoindentation test and surface roughness tester were used to evaluate the chemical structure, wear mechanisms of DLC coatings. This study proved that hardness reached up to 12.2 ± 1.11 GPa and the wear behavior was enhanced significantly by the DLC coating deposition. The mass loss increased with a rise in the duty cycle. Increasing the Argon/Methane ratio from 4:1 to 6:1 caused a decrease in the mass loss of DLC coatings. Burnishing, pulling out and adhesive wear were the dominant mechanisms.     

Resistance of pure and mixed rare earth silicates against calcium-magnesium-aluminosilicate (CMAS): A comparative study

Rare earth silicate environmental barrier coatings (EBCs) are state of the art for protecting SiC ceramic matrix composites (CMCs) against corrosive media. The interaction of four pure rare earth silicate EBC materials Yb₂SiO₅, Yb₂Si₂O₇, Y₂SiO₅, Y₂Si₂O₇ and three ytterbium silicate mixtures with molten calcium-magnesium-aluminosilicate (CMAS) were studied at high temperature (1400°C). The samples were characterized by SEM and XRD in order to evaluate the recession of the different materials after a reaction time of 8 hours. Additionally, the coefficient of thermal expansion (CTE) was determined to evaluate the suitability of Yb silicate mixtures as EBC materials for SiC CMCs. Results show that monosilicates exhibit a lower recession in contact with CMAS than their disilicate counterparts. The recession of the ytterbium silicates is far lower than the recession of the yttrium silicates under CMAS attack. Investigation of the ytterbium silicate mixtures exposes their superior resistance to CMAS, which is even higher than the resistance of the pure monosilicate. Also their decreased CTE suggests they will display better performance than the pure monosilicate.     

Relationship between electrical and mechanical loss tangents of hollow glass powder reinforced epoxy composites: A pilot study

This study was focused on the synthesis of monodisperse poly(n‐butyl methacrylate‐co‐methyl methacrylate) submicrospheres via soap‐free emulsion polymerization and on their characterization. The glass‐transition temperatures of poly(n‐butyl methacrylate) and poly(methyl methacrylate) were approximately 25 and 110°C, respectively. Therefore, submicrospheres with different glass‐transition temperatures could be obtained through the variation of the copolymer composition. In addition, relationships between the monomer feed concentration (M₀) and the Mark–Houwink constant (α) for the copolymer submicrospheres were proposed. The molecular weights of the copolymer submicrospheres decreased sharply with an increase in the weight fraction of n‐butyl methacrylate. On the contrary, the particle diameter increased linearly from 277 to 335 nm with an increase in the weight fraction of n‐butyl methacrylate. The α values decreased with an increase in M₀, and this indicated that the branched structures of the copolymer submicrospheres were easily obtained when M₀ was higher than 0.11 g/mL of water. Consequently, the results of this study are expected to provide useful information for the synthesis of monodisperse copolymer submicrospheres by soap‐free emulsion polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High temperature anti‐oxidation behavior of in situ and ex situ nanostructured C/SiC/ZrB2‐SiC gradient coatings: Thermodynamical evolution,microstructural characterization,and residual stress analysis

Nanostructured C/SiC/ZrB₂–SiC oxidation protective gradient coating was prepared by a two‐step reactive melt infiltration method. In order to reduce production cost, ZrB₂ phase was synthesized by the in situ reactive that included low‐cost ZrO₂ and B₂O₃ powders as raw materials. High‐temperature oxidation behavior of coatings was evaluated by isothermal oxidation test at 1773 K in air for 10 hours. Thermodynamical behavior of the coatings at various temperatures during oxidation test and coating process was predicted by HSC Chemistry 6.0 software. Compressive residual stresses of 36.9 MPa and 41 MPa were calculated for in situ and ex situ coatings by Williamson‐Hall method. After 10 hours of isothermal oxidation at 1773K, in situ and ex situ coatings showed 12.84% and 15.69% of weight losses with oxidation rates of 1.87 × 10^?2 g cm^?3 h^?1 and 0.91 × 10^?2 g cm^?3 h^?1, respectively. These results indicated that the oxidation protection ability of the coating produced by the in situ method was very close to ex situ coating.     

A comparative study of physical properties in Fe3O4 nanoparticles prepared by coprecipitation and citrate methods

Magnetite exhibits unique structural, electronic, and magnetic properties in extreme conditions that are of great research interest. In this work, the effects of preparation technique on X‐ray peak broadening, magnetic and elastic moduli properties of Fe₃O₄ nanoparticles prepared by coprecipitation (FcP‐NPs) and citrate (FC‐NPs) methods have been investigated. The structural characterization of the samples is evidence for a cubic structure with Fd‐3m space group. The Williamson‐Hall analysis was used to study crystallite sizes and lattice strain of the samples and also stress and energy density. In addition, the crystallite sizes are compared with the particle sizes and the magnetic core sizes obtained from TEM and VSM methods, respectively. In addition, the cation distribution obtained from calculated inversion parameter indicate that in the smaller particles, more amount of Fe²⁺ on the tetrahedral sites can be related to higher stress induced in the FcP‐NPs compared to the FC‐NPs. The saturation magnetization of the FcP‐NPs is almost two times bigger than the saturation magnetization of the FC‐NPs. It could be attributed to the decrease in the negative interaction on the octahedral site and also the magnetic moment on the tetrahedral site of the FcP‐NPs. The increase in force constants of the FC‐NPs determined by infrared spectra analysis compared to FcP‐NPs suggests the strengthening of their interatomic bonding. The values of shear and longitudinal wave velocities obtained from force constants have been used to determine the values of Young's modulus, rigidity modulus, bulk modulus, and Debye temperature. By comparison of the elastic results of FC‐NPs with the FcP‐NPs, we can observe that the elastic properties of the F‐NPs have been improved by synthesis method, while Poisson's ratio almost remains constant. In addition, using the values of the compliance s_ij obtained from elastic stiffness constants, the values of Young's modulus and Poisson's ratio along the oriented direction [hkl] have been calculated for the samples.     

A comparative study of thermal conductivity and thermal emissivity of high temperature solar absorber of ZrO2 /Fe2O3 and Al2O3/CuO ceramics

Oxide ceramics are considered as promising high temperature solar absorber materials. The major aim of this work is the development of a new solar absorber material with promising characteristics, high efficiency and low-cost processing. Hence, this work provides a comparative and inclusive study of densification behavior, microstructure features, thermal emissivity and thermal conductivity values of the two new high temperature solar absorbers of ZrO₂/Fe₂O₃ and Al₂O₃/CuO ceramics. Ceramic composites of ZrO₂/(10–30 wt%) Fe₂O₃ and Al₂O₃/(10–30 wt%) CuO were prepared by pressureless sintering method at a temperature of 1700 °C/2hrs. Identification of the solar to thermal efficiency of the composites was evaluated in terms of their measured thermal emissivity. Thermal efficiency and heat transfer homogeneity were investigated in terms of thermal conductivity and diffusivity measurement. The results showed that both composites exhibited comparable densification behavior, homogenous and harmonious microstructure. However, Al₂O₃/10 wt% CuO composite showed higher thermal and solar to thermal efficiencies than ZrO₂/Fe₂O₃ composites. It gave the lowest and the best thermal emissivity of 0.561 and the highest thermal conductivity of 15.4 W/m. K. These values proved to be the best amongst all those of the most known solar absorber materials made from the expensive SiC and AlN ceramics. Thus, Al₂O₃/CuO composites have succeeded in obtaining outstanding properties at a much lower price than its other competitive materials. These results may strongly identify Al₂O₃/CuO composites as promising high-temperature solar absorber materials instead of ZrO₂ and the other carbide and nitride ceramics.     

A comparative study between experimentally measured mechanical attributes and users’ perception of soft feel coatings: Correlating human sense with surface characteristics of polyurethane based coatings

Different soft feel coating formulations using waterborne resins composed of soft and hard polyurethane resins were prepared. The effects of resins mixtures on the soft feel properties were studied. Attempts were made to find out the correlation between users perception and experimentally measured surface characteristics of the coatings. To this end, 72 people were asked to touch the coatings in a similar testing environment and to express their feeling in order to rank them between 1 (lowest soft feel effect) and 4 (highest soft feel effect). The coatings physical characteristics were studied by tensile test, micro Vickers hardness, atomic force microscope (AFM) and friction coefficient measurement. It was shown that the mixtures of 25:75 of soft and hard resins resulted in the best soft feel effect. Users did not consider low or high hardness films as soft. Instead, those coatings having greater toughness were ranked as the best soft feel effect. Also, coatings with lower friction coefficient and lower surface roughness were preferred by users. However, the lowest friction coefficient did not result in the best soft feel appeal. In fact, the mechanical properties, surface roughness and friction coefficient were found to play as the criteria to show soft feel effect. It is thus concluded that by selecting appropriate surface characteristics of coatings related to soft feel effect, good agreement between these properties and human feeling can be made.     

A comparative investigation on microstructure evolution and wear resistance of in situ synthesized NbC,WC, TaC reinforced Mo2FeB2 coatings by laser cladding

To improve the microhardness and wear resistance of Mo₂FeB₂ coatings, composite coatings were prepared by laser cladding using in situ synthesized NbC, WC, and TaC. The influence of different carbides on the morphology, microstructure, microhardness, residual stress, and tribological properties of the composite coatings was investigated. The results showed various microstructural morphologies in different composite coatings. Apparent herringbone structures were observed in most coatings except for the Mo₂FeB₂/TaC composite coating and a eutectic structure was formed in the Mo₂FeB₂/WC composite coating. In addition, the heat-affected zone was typically composed of acicular martensite and lath martensite. The microhardness of the Mo₂FeB₂/WC composite coating increased to 1543.6 HV_0.5 compared with 985.7 HV_0.5 observed for the Mo₂FeB₂ coating. Tensile stress existed in the coating, bonding zone, and heat-affected zone, whereas the substrate exhibited compressive stress. The Mo₂FeB₂/WC composite coating exhibited the lowest tensile stress (298 MPa). The Mo₂FeB₂/WC composite coating containing WC and the W₂C phase had the lowest coefficient of friction (0.38) and wear rate (3.90 × 10^?5 mm³/Nm), indicating its excellent tribological properties. Moreover, the wear mechanism of the Mo₂FeB₂ coating is severe adhesive and abrasive wear. The adhesive wear mechanism was mitigated by the formation of in situ synthesized NbC, WC, and TaC. The wear mechanism of the Mo₂FeB₂/WC composite coating was only a slight abrasive wear.     

Synthesis and magnetic properties of nano-sized Cu0.5Ni0.5Fe2O4 via citrate and aloe vera: A comparative study

In this report, Cu_0.5Ni_0.5Fe₂O₄ nanoparticles were synthesized by solgel using eco-friendly aloe vera extract and citric acid separately and their properties were discussed. Structural, Functional, morphological, magnetic properties of the samples were characterized using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscopy (TEM), Vibrating sample magnetometer (VSM). XRD exhibited the samples have single phase cubic spinel with average size of 46.4?nm and 35.45?nm. Two characteristics bands of ferrite were confirmed by FTIR. TEM indicated different morphology of the samples with some regularity. VSM data showed that higher coercivity for the sample prepared by aloe vera extract.     

A comparative study on the selective hydrogenation of α,β unsaturated aldehyde and ketone to unsaturated alcohols on Au supported catalysts

The hydrogenation of trans,4-phenyl,3-buten,2-one (benzalacetone) and trans,3-phenyl, propenal (cinnamaldehyde) was carried out on Au supported on iron oxides catalysts. Commercial goethite (FeOOH), maghemite (γFe₂O₃) and hematite (αFe₂O₃) were used as supports. The catalytic activity of Au/Fe₂O₃ reference catalyst, supplied by the World Gold Council, was also investigated. Gold catalysts and the parent supports were characterized by BET, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of ammonia (NH₃-TPD) and high resolution transmission electron microscopy (HRTEM).Among the catalysts investigated Au supported on FeOOH shows the highest activity and selectivity to UA in the hydrogenation of unsaturated carbonyl compounds whereas Au supported on αFe₂O₃ are the less active and selective catalysts.The catalytic activity and selectivity to unsaturated alcohols (UA) in the hydrogenation of benzalacetone and cinnamaldehyde are less influenced by the morphology of gold particles and are mainly influenced by the nature of the support.A correlation between the reducibility of the catalysts and the activity and selectivity to UA has been found. Increasing the reducibility of the catalysts both the activity and selectivity to UA increase. These results let us to argue that active and selective sites are formed by negative gold particles formed through the electron transfer from the reduced support to the metal.     

Preparation of multifunctional thiol‐ and acrylate‐terminated polyurethane: A comparative study on their properties in UV curable coatings

The multifunctional thiol‐ and acrylate‐terminated polyurethane (PU) has been successfully prepared for using as the main resin in the UV curable coatings. The structure and molecule weight of prepared PUs were analyzed by fourier transformed infrared spectroscopy (FTIR) and gel permeation chromatography, respectively. The results showed that the different terminal multifunctional groups have been grafted onto the PU and their difference in molecule weight was significant. Used as the main resin in coatings, the curing kinetic and percentage conversion of the different UV curing coatings system were investigated by real‐time FTIR method, and the effects of terminal functional groups and photoinitiator on the final conversion percentage and conversion rate were also compared. It is observed that the thiol‐terminated PU had higher conversion speed and final conversion percentage due to the remarkable effect of mercapto groups on reducing oxygen inhibition during UV curing process. The shrinkage, viscosity, and adhesion of UV curable coatings with thiol‐ and acrylate‐terminated PUs were also investigated and compared, and the results indicated that the former exhibited lower shrinkage and higher adhesion performances than the latter, along with the lower viscosity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40740.     

An FTIR/ATR in situ study of sorption and transport in corrosion protective organic coatings: Paper 2. The effects of temperature and isotopic dilution

A detailed temperature variation (18–50 °C) FTIR/ATR study of sorption and desorption of water into a series of cured epoxy resins has been reported. For higher temperatures (35–50 °C) the data were modelled with a single Fickian diffusion equation, giving an increased D as the temperature increased and an activation energy (E_A) in the 55–60 kJ mol⁻¹ region. At lower temperatures (18–35 °C)—well-below the T_g—a two-stage sorption equation was needed and the apparent E_A was negative. This is probably associated with changes in water clustering among the distributed ‘voids’ in the glassy polymer associated with chain relaxation at extended times. The use of D₂O as a penetrant allowed diffusion coefficient measurements for highly dense epoxy matrices, where FTIR/ATR cannot detect the ν(OH) band of water over and above the residual polymer–OH groups (in the dry state). The data for the D₂O studies were notably influenced by isotopic exchange; which was found to be a diffusion controlled process, even in a polymer matrix.     

Structure and crystallization behavior of complex mold flux glasses in the system CaO-Na2O-Li2O-CaF2-B2O3-SiO2: A multi-nuclear NMR spectroscopic study

The structure of mold flux glasses in the system CaO-(Na,Li)₂O-SiO₂-CaF₂ with unusually high modifier contents, stabilized by the addition of ∼4 mol% B₂O₃, is studied using ⁷Li, ²³Na, ¹⁹F, ¹¹B, and ²⁹Si magic-angle-spinning (MAS), and ⁷Li{¹⁹F} and ²³Na{¹⁹F} rotational echo double-resonance (REDOR) nuclear magnetic resonance (NMR) spectroscopy. When taken together, the spectroscopic results indicate that the structure of these glasses consists primarily of dimeric [Si₂O₇]⁻⁶ units that are linked to the (Ca,Na,Li)-O coordination polyhedra, and are interspersed with chains of corner-shared BO₃ units. The F atoms in the structure are exclusively bonded to Ca atoms, forming Ca(O,F)_n coordination polyhedra. This structural scenario is shown to be consistent with the crystallization of cuspidine (3CaO·2SiO₂·CaF₂) from the parent melts on slow supercooling. The progressive addition of Li to a Na-containing base composition results in a corresponding increase in the undercooling required for the nucleation of cuspidine in the melt, which is attributed to the frustrated local structure caused by the mixing of alkali ions.     

A comparative study of the water-gas shift activity of Pt catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide carriers

The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MO_x/Al₂O₃ and MO_x/TiO₂ supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H₂O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts, it is shown that the presence of MO_x results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al₂O₃ or Pt/TiO₂, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MO_x. Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H₂O, 20% H₂ and 6% CO₂, showed that certain composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications.