Synthesis of lanthanum zirconium oxide nanomaterials through composite-hydroxide-mediated approach

A novel thermal barrier coating material, lanthanum zirconium oxide (La₂Zr₂O₇) has been synthesized through the composite-hydroxide-mediated method at low temperature. The phase structures, morphology, thermal stability and thermal conductivity of the as-synthesized La₂Zr₂O₇ were investigated systematically. The X-ray diffraction (XRD) patterns revealed a single phase with cubic pyrochlore structure for La₂Zr₂O₇ after treated at 1300 °C for 100 h. The transmission electron microscope (TEM) and scanning electron microscope (SEM) analyses showed that the sample was made up of sphere-like nanoparticles with the size between 50 and 100 nm. Furthermore, the thermal analysis result demonstrated the La₂Zr₂O₇ sample had high thermal stability even at 1300 °C. As the temperature increased to 1200 °C, the thermal conductivity value could be as low as 1.75 W m^?1 K^?1. Due to the high-temperature stability and lower thermal conductivity, the La₂Zr₂O₇ material is expected to be a promising candidate for the use of thermal barrier coatings.     

Improving the hot corrosion resistance of plasma sprayed ceria–yttria stabilized zirconia thermal barrier coatings by laser surface treatment

Ceria–yttria stabilized zirconia (CYSZ) thermal barrier coatings (TBCs) were deposited by air plasma spraying on NiCoCrAlY-coated Inconel 738LC substrates. After that, the surface of plasma sprayed CYSZ TBCs were glazed using a pulsed Nd:YAG laser. The effects of laser glazing on hot corrosion resistance of the coatings were evaluated in presence of 45 wt%Na₂SO₄ + 55 wt%V₂O₅ corrosive molten salt at 1000 °C. The results revealed that the hot corrosion resistance of plasma sprayed CYSZ TBCs were enhanced more than twofold by laser surface glazing due to reducing specific reactive area of the dense glazed surface layer and consequently, decreasing the reaction between molten salt and zirconia stabilizers.     

Formation and thermal properties of fluorite-pyrochlore composite structure in La2(ZrxCe1 − x)2O7 oxide system

Rare-earth oxides of La₂(Zr_xCe_1 ? x)₂O₇ for thermal barrier coatings (TBCs) are fabricated via a solid-state reaction at 1600 °C. As the phase formation, microstructure, and thermal properties of these oxides are examined, a fluorite–pyrochlore composite structure is found in the La₂(Zr_xCe_1 ? x)₂O₇ system. This composite structure is composed of coarse Ce-rich fluorite and fine Zr-rich pyrochlore grains. From XRD and microstructural analysis, the lattice parameter and volume fraction of each phase are evaluated in order to obtain the intrinsic thermal conductivity value of composite-structured oxide with porosity calibration. The thermal conductivity of the composite structure is similar to that of pyrochlore La₂Zr₂O₇, which is attributed to phonon scattering by phase boundaries.     

Investigation of La3 + Doped Yb2Sn2O7 as new thermal barrier materials

Low thermal conductivity is one of the key requirements for thermal barrier coating materials. From the consideration of crystal structure and ion radius, La^3 + Doped Yb₂Sn₂O₇ ceramics with pyrochlore crystal structures were synthesized by sol–gel method as candidates of thermal barrier materials in aero-engines. As La^3 + and Yb^3 + ions have the largest radius difference in lanthanoid group, La^3 + ions were expected to produce significant disorders by replacing Yb^3 + ions in cation layers of Yb₂Sn₂O₇. Both experimental and computational phase analyses were carried out, and good agreement had been obtained. The lattice constants of solid solution (La_xYb_1 − x)₂Sn₂O₇ (x = 0.3, 0.5, 0.7) increased linearly when the content of La^3 + was increased. The thermal properties (thermal conductivity and coefficients of thermal expansion) of the synthesized materials had been compared with traditional 8 wt.% yttria stabilized zirconia (8YSZ) and La₂Zr₂O₇ (LZ). It was found that La^3 + Doped Yb₂Sn₂O₇ exhibited lower thermal conductivities than un-doped stannates. Amongst all compositions studied, (La_0.5Yb_0.5)₂Sn₂O₇ exhibited the lowest thermal conductivity (0.851 W·m^− 1·K^− 1 at room temperature), which was much lower than that of 8YSZ (1.353 W·m^− 1·K^− 1), and possessed a high coefficient of thermal expansion (CTE), 13.530 × 10^− 6 K^− 1 at 950 °C.     

Preparation,structure and electrical conductivity of pyrochlore-type samarium–lanthanum zirconate ceramics

A series of zirconate compounds with the general formula Sm_2–xLa_xZr₂O₇ (0 ? x ? 1.0) were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, structure and electrical conductivity of Sm_2–xLa_xZr₂O₇ ceramics were investigated by the Archimedes method, X-ray diffraction and impedance spectroscopy measurements. Sm_2–xLa_xZr₂O₇ (0 ? x ? 1.0) ceramics exhibit a pyrochlore-type structure. The measured electrical conductivity of Sm_2–xLa_xZr₂O₇ ceramics obeys the Arrhenius relation and gradually increases with increasing temperature from 673 to 1173 K. Sm_2–xLa_xZr₂O₇ ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10^?4 to 1.0 atm at all test temperature levels. The electrical conductivity of Sm_2–xLa_xZr₂O₇ ceramics decreases with increasing lanthanum content at identical temperature levels.     

Low-temperature synthesis of Li7La3Zr2O12 with cubic garnet-type structure

In this paper, we report the direct synthesis of Li₇La₃Zr₂O₁₂ with the cubic garnet-type structure at low temperature with a lattice constant of 13.0035 Å. The synthesis condition is optimized to be at 750 °C for 8 h with 30 wt% excess lithium salt. No intermediate grinding was involved in this straightforward route. Without the adventitious of Al³⁺, the cubic Li₇La₃Zr₂O₁₂ is unstable above 800 °C and has an ionic conductivity of the order of 10^?6 S cm^?1.     

The hot corrosion of 310 stainless steel with pre-coated NaCl/Na2SO4 mixtures at 750 °C

The high-temperature corrosion behavior of 310 stainless steel has been studied at 750 °C in air with 2 mg cm⁻² mixtures of various NaCl/Na₂SO₄ ratios. The corrosion behavior and morphological development were investigated by weight gain kinetics, metallographs, depths of attack, metal losses, and X-ray analyses. The results show that weight gain kinetics in simple oxidation reveals a steady-state parabolic rate law after 3 h, while the kinetics with salt deposits display multi-stage growth rates. NaCl is the main corrosive specie in high-temperature corrosion involving mixtures of NaCl/Na₂SO₄ and is responsible for the formation of internal attack. The most severe corrosion takes place with the 75% NaCl mixtures. Uniform internal attack is the typical morphology of NaCl-induced hot corrosion, while the extent of intergranular attack is more pronounced as the content of Na₂SO₄ in the mixture is increased.     

Effects of La2O3 on microstructure and wear properties of laser clad γ/Cr7C3/TiC composite coatings on TiAl intermatallic alloy

The effects of La₂O₃ addition on the microstructure and wear properties of laser clad γ/Cr₇C₃/TiC composite coatings on γ-TiAl intermetallic alloy substrates with NiCr–Cr₃C₂ precursor mixed powders have been investigated by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive spectrometer (EDS) and block-on-ring wear tests. The responding wear mechanisms are discussed in detail. The results are compared with that for composite coating without La₂O₃. The comparison indicates that no evident new crystallographic phases are formed except a rapidly solidified microstructure consisting of the primary hard Cr₇C₃ and TiC carbides and the γ/Cr₇C₃ eutectics distributed in the tough γ nickel solid solution matrix. Good finishing coatings can be achieved under a proper amount of La₂O₃-addition and a suitable laser processing parameters. The additions of rare-earth oxide La₂O₃ can refine and purify the microstructure of coatings, relatively decrease the volume fraction of primary blocky Cr₇C₃ to Cr₇C₃/γ eutectics, reduce the dilution of clad material from base alloy and increase the microhardness of the coatings. When the addition of La₂O₃ is approximately 4 wt.%, the laser clad composite coating possesses the highest hardness and toughness. The composite coating with 4 wt.%La₂O₃ addition can result the best enhancement of wear resistance of about 30%. However, too less or excessive addition amount of La₂O₃ have no better influence on wear resistance of the composite coating.     

Effect of the composition profile and density of LPPS sprayed functionally graded coating on the thermal shock resistance

Low Pressure Plasma Spraying (LPPS) is a promising coating method for Functionally Graded Material (FGM) expected to be able to reduce the thermal stress in high temperature environments such as a gas turbine. In this paper, we report the effect of the composition profile and coating density of LPPS sprayed FGM, consisting of ZrO₂–8 wt%Y₂O₃ (YSZ) top coating, YSZ–Ni–20 wt%Cr (NiCr) FGM coating, NiCr under coating and copper substrate, on the thermal shock resistance evaluated by a modified temperature difference test. The density of YSZ and NiCr coating was successfully controlled by the chamber pressure and initial particle size in the range from 5.43 to 5.79 g/cm³ and from 7.89 to 8.09 g/cm³, respectively. For an YSZ composition profile from NiCr under coating to YSZ top coating (in FGM), the highest thermal shock resistance was obtained when the fraction of YSZ increased with gentle slope just over NiCr coating and acute slope just under YSZ coating. Also, the higher density coatings tended to perform the higher thermal shock resistance. Initial cracks formed in the YSZ top coating propagated into YSZ parts in FGM coating through the grain boundary of YSZ and/or the interface between flattened NiCr and YSZ particles. After the cracks connected, the coupled cracks caused the coating spallation.     

Adhesive strength of new thermal barrier coatings of rare earth zirconates

La₂Zr₂O₇ (LZ) and La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) as novel candidate materials for thermal barrier coatings (TBCs) were prepared by electron beam-physical vapor deposition (EB-PVD). The adhesive strength of the as-deposited LZ and LZ7C3 coatings were evaluated by transverse scratch test. Meanwhile, the factors affecting the critical load value were also investigated. The critical load value of LZ7C3 coating is larger than that of LZ coating, whereas both values of these two coatings are lower than that of the traditional coating material, i.e. 8 wt% yttria stabilized zirconia (8YSZ). The micro-cracks formed in the scratch channel can partially release the stress in the coating and then enhance the adhesive strength of the coating. The width of the scratch channel and the surface spallation after transverse scratch test are effective factors to evaluate the adhesive strength of LZ and LZ7C3 coatings.     

Wear behaviors of Fe-based amorphous composite coatings reinforced by Al2O3 particles in air and in NaCl solution

In this paper, the influence of the addition of Al₂O₃ particles on the microstructure and wear properties of Fe-based amorphous coatings prepared by high velocity oxygen fuel (HVOF) has been studied. The wear behaviors of the composite coatings were evaluated against Si₃N₄ in a pin-on-disk mode in air and in 3.5 wt.% NaCl solution. It was found that the Al₂O₃ particles were homogenously distributed in the amorphous matrix and the composite coatings exhibited improved wear resistance and reduced coefficient of friction (COF) in both air and wet conditions as compared to the monolithic amorphous coating. The composite coating reinforced with 20 wt.% Al₂O₃ particles exhibit the best wear performance, which, for example, has extremely low COF (< 0.2) and high wear resistance (2–3 times higher than monolithic amorphous coating). Detailed analysis on the worn surface indicated that the wear mechanism for the amorphous and composite coatings is similar and is dominated by oxidative delamination in air and by corrosion wear in 3.5% NaCl solution. The enhanced wear resistance is mainly attributed to the addition of Al₂O₃ particles which exhibit high hardness, good corrosion resistance and excellent chemical and thermal stability.     

Effect of deflocculants on hardness and densification of YSZ–Al2O3 (whiskers & particulates) composites

In the present study effect of deflocculants like P-Aminobenzoic Acid (PABA) and Cetyltrimethyl ammonium bromide (CTAB) on densification and hardness of 3 mol.% Yttria-stabilized ZrO₂ (abridged as YSZ) + Al₂O₃ (whiskers or particulates) composite have been studied. Maximum hardness & density were achieved at 1 wt% of CTAB or PABA, while further addition (5, 10 and 15 wt%) had no significant affect on the aforementioned properties. It was also observed that alumina addition in form of particulates only improved the density while its addition in form of whiskers significantly increased the hardness of YSZ + alumina composite. The maximum hardness achieved was more than 14 GPa in case of sample containing alumina in form of whiskers.     

Effects of heat treatment on adhesion strength of thermal barrier coating systems

Thermal barrier coatings (TBCs) are widely used as protective and insulative coatings on hot section components of gas turbines and their applications, like blades and combustion chambers. The quality and performance properties of TBCs are of great importance in terms of their resistance to service conditions. In a TBC system, there is a close relationship between the adhesion properties of coating layers. The adhesion strength of TBCs varies depending on the coating technique used and the surface treatments. In this study, CoNiCrAlY and YSZ (ZrO₂ + Y₂O₃) powders were deposited on stainless steel substrate. High Velocity Oxy-Fuel (HVOF) and Atmospheric Plasma Spraying (APS) techniques were used to produce the bond coats. The ceramic top layers on CoNiCrAlY bond coats were produced by the APS technique. The TBC specimens were subjected to heat-treatment tests. Adhesion strength for top coat/bond coat interface of as-sprayed and heat-treated samples was investigated. The results showed that the heat treatment of the coatings in different temperatures led to an increase in the adhesion strength of TBCs.     

Nanocomposite protective coatings based on Ti–N–Cr/Ni–Cr–B–Si–Fe,their structure and properties

The first results of manufacturing and investigations of a new type of nanocomposite protective coatings are presented. They were manufactured using a combination of two technologies: plasma-detonation coating deposition with the help of plasma jets and thin coating vacuum-arc deposition. We investigated structure, morphology, physical and mechanical properties of the coatings of 80–90 μm thickness, as well as defined the hardness, elastic Young modulus and their corrosion resistance in different media. Grain dimensions of the nanocomposite coatings on Ti–N–Cr base varied from 2.8 to 4 nm. The following phases and compounds formed as a result of plasma interaction with the thick coating surface were found in the coatings: Ti–N–Cr (200), (220), γ-Ni₃–Fe, a hexagonal Cr₂–Ti, Fe₃–Ni, (Fe, Ni)N and the following Ti–Ni compounds: Ti₂Ni, Ni₃Ti, Ni₄Ti, etc. We also found that the nanocomposite coating microhardness increased to H = 31.6 ± 1.1 GPa. The Young elastic modulus was determined to be E = 319 ± 27 GPa – it was derived from the loading–unloading curves. The protective coating demonstrated the increased corrosion resistance in acidic and alkaline media in comparison with that of the stainless steel substrate.     

Characteristics and performance of hard Ni60 alloy coating produced with supersonic laser deposition technique

A novel coating fabrication technique, known as supersonic laser deposition (SLD), which combines cold spray (CS) with laser technology, is applied to produce hard Ni60 (58–62 HRC) coating on medium carbon steel (AISI 1045 steel) substrate. Different process parameters are investigated to obtain the optimal. The Ni60 coating specimens prepared by SLD process are studied microstructurally using scanning electron microscope (SEM), energy dispersive spectrum (EDS) and X-ray diffraction (XRD). The microstructures of the coatings are compared with those of the coatings produced using laser cladding (LC). The hardness, tribological property and corrosion resistance of the Ni60 coatings produced by SLD and LC with the optimal process parameters are evaluated under Vickers hardness, pin-on-disk wear and electrochemical corrosion tests. It is demonstrated that the Ni60 coating with SLD exhibits some characteristics, such as fine microstructure as cast, stable phases and less dilution; it surpasses the coating produced with conventional LC process in sliding wear resistance; but in 1 mol/L H₂SO₄ solution, the SLD and LC coatings performed similarly in corrosion resistance. This research has proved that SLD technique enables depositing hard Ni60 on steel substrate, which is impossible for CS technique.     

Development of mixed conducting dense nickel/Ca-doped lanthanum zirconate cermet for gas separation application

La_1.95Ca_0.05Zr₂O_7-δ (LCZ) and Ni–LCZ cermet have been prepared by combustion synthesis and conventional solid state mixing methods respectively. Both the materials are sintered in air and controlled atmosphere (5% H₂ in Ar). The density obtained for the material sintered at 1400 °C in controlled atmosphere is found to be more than 99.5%. This sintering temperature (1400 °C) is considered to be much lower compared to the conventional sintering temperature. The corresponding total conductivity for such Ni–LCZ cermet materials is ～400 S/cm measured at 750 °C having 40 vol% of Ni and 60 vol% LCZ.     

Facile synthesis of cubic fluorite nano-Ce1−xZrxO2 via hydrothermal crystallization method

Nano-Ce_1?xZr_xO₂ (x = 0.15, 0.25, 0.5) were synthesized via co-precipitation using NH₄OH as precipitant and hydrothermal crystallization. The XRD results confirmed that the cubic fluorite nano-Ce_1?xZr_xO₂ can form in NH₄OH solution (pH > 10) at 150 °C for 12 h, and well crystallized 20–50 nm nano-Ce_1?xZr_xO₂ were obtained at 200 °C for 22 h. The crystal growth of Ce_1?xZr_xO₂ was suppressed under higher OH^? concentration and crystallite size decreased with increasing concentration of NH₄OH. Ce3d XP spectra showed that the main valence state of the cerium on Ce_1?xZr_xO₂ surface is +4, and substituting Ce⁴⁺ with Zr⁴⁺ has no obvious influence on Ce³⁺/Ce⁴⁺ ratio.     

Phase structure evolution and thermal expansion variation of Sc2O3 doped Nd2Zr2O7 ceramics

(Nd_1−xSc_x)₂Zr₂O₇ (x = 0, 0.1, 0.3, 0.5, 0.7) compounds were synthesized by solid state reaction at 1700 °C for 10 h, and characterized by XRD, Raman spectroscopy, SEM and high-temperature dilatometer. Nd₂Zr₂O₇ exhibited pyrochlore phase, and its lattice parameter increased after Sc₂O₃ doping, which could be attributed to the presence of Sc³⁺ interstitial ions in pyrochlore lattice. Fluorite phase formed in the doped Nd₂Zr₂O₇, and (Nd_0.3Sc_0.7)₂Zr₂O₇ exhibited pure fluorite phase. The thermal expansion coefficient (TEC) of Nd₂Zr₂O₇ was significantly enhanced by 10 mol% Sc₂O₃ doping, but higher Sc₂O₃ doping decreased the TEC. The reduced crystal energy due to the presence of Sc³⁺ interstitial ions could cause the initial increase in the TEC, and the formation of fluorite phase might contribute to the reduced TEC. Considering the alleviation of the thermal expansion mismatch stress for the high-temperature applications of Nd₂Zr₂O₇, Sc₂O₃ was an excellent dopant and there existed an optimal Sc₂O₃ content for the optimization design of compound compositions.     

Influence of heat treatment on microstructure and adhesion of Al2O3 fiber-reinforced electroless Ni–P coating on Al–Si casting alloy

Influence of heat treatment regime on microstructure, phase composition and adhesion of Al₂O₃ fiber-reinforced Ni–P electroless coating on an Al–10Si–0.3 Mg casting alloy is investigated in this work. The pre-treated substrate was plated using a bath containing nickel hypophosphite, nickel lactate and lactic acid. Al₂O₃ fibers pretreated with demineralised water were placed into the plating bath. Resulting Ni–P–Al₂O₃ coating thickness was about 12 μm. The coated samples were heat treated at 400–550 °C/1–8 h. LM, SEM, EDS and XRD were used to investigate phase transformations. Adhesion of coating was estimated using scratch test with an initial load of 8.80 N. It is found that annealing at high temperatures (450 °C and above) leads to the formation of hard intermetallic products (namely Al₃Ni and Al₃Ni₂ phases) at the substrate–coating interface. However, as determined by the light microscopy and by the scratch test, these phases reduce the coating adhesion (compared to coatings treated by the optimal annealing regime 400 °C/1 h). The analysis of scratch tracks proves that fiber reinforcement significantly reduces the coating scaling. However, due to the formed intermetallic sub-layers, partial coating delamination may occur on the samples annealed at 450 °C and above.     

Electrophoretic bilayer deposition of zirconia and reinforced bioglass system on Ti6Al4V for implant applications: An in vitro investigation

The physical, chemical and biological properties of the bioglass reinforced yttria-stabilized composite layer on Ti6Al4V titanium substrates were investigated. The Ti6Al4V substrate was deposited with yttria stabilized zirconia — YSZ as the base layer of thickness ≈ 4–5 μm, to inhibit metal ion leach out from the substrate and bioglass zirconia reinforced composite as the second layer of thickness ≈ 15 μm, which would react with surrounding bone tissue to enhance bone formation and implant fixation. The deposition of these two layers on the substrate was carried out using the most viable electrophoretic deposition (EPD) technique. Biocompatible yttria-stabilized zirconia (YSZ) in the form of nano-particles and sol gel derived bioglass in the form of micro-particles were chosen as precursors for coating. The coatings were vacuum sintered at 900 °C for 3 h. The biocompatibility and corrosion resistance property were studied in osteoblast cell culture and in simulated body fluid (SBF) respectively. Analysis showed that the zirconia reinforced bioglass bilayer system promoted significant bioactivity, and it exhibited a better corrosion resistance property and elevated mechanical strength under load bearing conditions in comparison with the monolayer YSZ coating on Ti6Al4V implant surface.