Thermal Spray Deposition,Phase Stability and Mechanical Properties of La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>/LaAlO<Subscript>3</Subscript> Coatings

This paper deals with the deposition of La₂Zr₂O₇ (LZO) and LaAlO₃ (LAO) mixtures by air plasma spray (APS). The raw material for thermal spray, single phase LZO and LAO in a 70:30 mol.% ratio mixture was prepared from commercial metallic oxides by high-energy ball milling (HEBM) and high-temperature solid-state reaction. The HEBM synthesis route, followed by a spray-drying process, successfully produced spherical agglomerates with adequate size distribution and powder-flow properties for feeding an APS system. The as-sprayed coating consisted mainly of a crystalline LZO matrix and partially crystalline LAO, which resulted from the high cooling rate experienced by the molten particles as they impact the substrate. The coatings were annealed at 1100 °C to promote recrystallization of the LAO phase. The reduced elastic modulus and hardness, measured by nanoindentation, increased from 124.1 to 174.7 GPa and from 11.3 to 14.4 GPa, respectively, after the annealing treatment. These values are higher than those reported for YSZ coatings; however, the fracture toughness (K _IC) of the annealed coating was only 1.04 MPa m^0.5.     

Phase Stability of Ce-Modified La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> Coatings and Chemical Compatibility with YSZ

Ce-modified La₂Zr₂O₇ powders, i.e., La₂Zr₂O₇ (LZ), La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3), and La₂(Zr_0.3Ce_0.7)₂O₇ (LZ3C7), were used to produce thermal barrier coatings by atmospheric plasma spray process. The chemical compatibility of the CeO₂-doped La₂Zr₂O₇ with the traditional YSZ was investigated in LZ-YSZ powder mixtures and LZ-YSZ bilayer coatings by x-ray diffraction and scanning electron microscope. The powder mixtures and coatings were aged at 1200 and 1300 °C for 100 h. The results showed that LZ and LZ7C3 presented single pyrochlore structure after the heat treatments at both 1200 and 1300 °C. For LZ3C7, however, fluorite structure was observed at 1300 °C, indicating a poor phase stability of LZ3C7 at the elevated temperature. The results further showed that La₂(Zr_0.3Ce_0.7)₂O₇ reacted with YSZ in the bilayer ceramic coatings due to the diffusion of cerium, zirconium, and yttrium. While for La₂Zr₂O₇(LZ) and La₂(Zr_0.7Ce_0.3)₂O₇, a better chemical compatibility with YSZ was shown.     

Mechanical Properties of LaTi<Subscript>2</Subscript>Al<Subscript>9</Subscript>O<Subscript>19</Subscript> and Thermal Cycling Behaviors of Plasma-Sprayed LaTi<Subscript>2</Subscript>Al<Subscript>9</Subscript>O<Subscript>19</Subscript>/YSZ Thermal Barrier Coatings

Recently, extensive efforts have been made to develop new thermal barrier coating (TBC) materials which can operate at temperatures above 1523 K over a long term. In this article, LaTi₂Al₉O₁₉ (LTA) was synthesized by solid-state reaction at 1773 K, and the mechanical properties of the LTA bulk were evaluated. The microhardness is about 14 GPa, comparable to that of YSZ bulk, whereas the Young’s modulus is about 44 GPa, lower than the value of YSZ. However, the fracture toughness of 0.8-1 MPa m^1/2 is much lower than that of bulk YSZ. A double-ceramic-layer LTA/YSZ TBC structure was proposed and the TBC sprayed by plasma spraying. Thermal cycling tests of the TBC specimens were performed at 1373 K with a dwell time of 10 min. The LTA remained good stability with ZrO₂ and Al₂O₃. However, the single layer LTA TBC was cracked at the LTA/bond coat interface after about 300 cycles, due to its poor thermal shock resistance, while the YSZ TBC yielded a lifetime of about 1000 cycles. The LTA/YSZ TBC remained intact even after 3000 cycles, exhibiting a promising potential as new TBC materials.     

Processing Parameter Effects and Thermal Properties of Y<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>7</Subscript> Nanostructured Environmental Barrier Coatings Synthesized by Solution Precursor Induction Plasma Spraying

The solution precursor plasma spray process, in which a solution of metal salts is axially injected into an induction thermal plasma, is suitable for deposition of nanostructured environmental barrier coatings. The effects of main processing parameters, namely the solution precursor concentration, spraying distance, reactor pressure, and atomization gas flow rate, have been analyzed using D-optimal design of experiments regarding the deposition rate and coating porosity responses. Among these four parameters, the solution precursor concentration had the greatest influent on the coating structure, followed by the spraying distance and reactor pressure, and finally the atomization gas flow rate with a small contribution. It is pointed out that the species that impact on the substrate are agglomerates of nanoparticles. The equivalent thermal conductivity of selected coatings was computed from experimental temperature evolution curves obtained by laser flash thermal diffusivity analysis, using two methods: a multilayer finite-element model with optimization, and a multilayer thermal diffusion model. The results of the two models agree, with coatings exhibiting low thermal conductivity between 0.7 and 1 W/(m K) at 800 °C.     

Yb<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>7</Subscript> Environmental Barrier Coatings Deposited by Various Thermal Spray Techniques: A Preliminary Comparative Study

Dense, crack-free, uniform, and well-adhered environmental barrier coatings (EBCs) are required to enhance the environmental durability of silicon (Si)-based ceramic matrix composites in high pressure, high gas velocity combustion atmospheres. This paper represents an assessment of different thermal spray techniques for the deposition of Yb₂Si₂O₇ EBCs. The Yb₂Si₂O₇ coatings were deposited by means of atmospheric plasma spraying (APS), high-velocity oxygen fuel spraying (HVOF), suspension plasma spraying (SPS), and very low-pressure plasma spraying (VLPPS) techniques. The initial feedstock, as well as the deposited coatings, were characterized and compared in terms of their phase composition. The as-sprayed amorphous content, microstructure, and porosity of the coatings were further analyzed. Based on this preliminary investigation, the HVOF process stood out from the other techniques as it enabled the production of vertical crack-free coatings with higher crystallinity in comparison with the APS and SPS techniques in atmospheric conditions. Nevertheless, VLPPS was found to be the preferred process for the deposition of Yb₂Si₂O₇ coatings with desired characteristics in a controlled-atmosphere chamber.     

Development of a Thermal Transport Database for Air Plasma Sprayed ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Thermal Barrier Coatings

Thermal diffusivities of air plasma sprayed (APS) thermal barrier coatings (TBCs) were measured by the laser flash method. The data were used to calculate thermal conductivity of TBCs when provided with density and specific heat data. Due to the complicated microstructure and other processing-related parameters, thermal diffusivity of TBCs can vary as much as three- to four-fold. Data collected from over 200 free-standing ZrO₂-7-8wt.%Y₂O₃ TBCs are presented. The large database gives a clear picture of the expected “band” of thermal diffusivity values. When this band is used as a reference for thermal diffusivity of a specific TBC, the thermal transport property of the TBC can be more precisely described. This database is intended to serve researchers and manufacturers of TBCs as a valuable resource for the evaluation of TBCs.     

Effects of La<Subscript>2</Subscript>O<Subscript>3</Subscript> on Mechanical Properties and Corrosion Resistance of H62 Brass

In this article, the effects of lanthanum oxide (La₂O₃) on the microstructure and mechanical properties of H62 brass were investigated by using the universal testing machine, Brinell hardness tester, optical microscope, and scanning electron microscope (SEM). Immersion corrosion and electrochemical measurements were carried out to identify the influence of La₂O₃ on the corrosion behavior of the H62 brass. The phase constitution, microstructure, and phase composition of the H62 brass were analyzed by x-ray diffraction, SEM, and energy-dispersive spectrometer, respectively. The results show that the microstructure of α phase changes from dendrite grains to equiaxed grains, and the content and distribution of β phase are improved significantly. When the La₂O₃ content reaches 0.8 wt.%, the H62 brass obtains favorable comprehensive mechanical properties and the strength and hardness decrease but elongation increases, which is conducive to plastic processing. In addition, under the optimum amount of 0.8 wt.% La₂O₃ content, the corrosion rate of immersion corrosion attains the minimum values: As 12.6 g m^?2 h^?1, it decreases by 24%; as the corrosion potential changes from ?1.1327 V to ?0.328 V, it increases by 70.9%; and as the corrosion current density decreases from ?2.833 mA mm^?2 to ?3.28 mA mm^?2 corrosion, it decreases by 15.78%, when compared with H62 brass.     

Microstructure and Thermal Properties of Atmospheric Plasma-Sprayed Yb<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>7</Subscript> Coating

In the present work, Yb₂Si₂O₇ powder was synthesized by solid-state reaction using Yb₂O₃ and SiO₂ powders as starting materials. Atmospheric plasma spray technique was applied to fabricate Yb₂Si₂O₇ coating. The phase composition and microstructure of the coating were characterized. The density, open porosity and Vickers hardness of the coating were investigated. Its thermal stability was evaluated by thermogravimetry and differential thermal analysis (TG-DTA). The thermal diffusivity and thermal conductivity of the coating were measured. The results showed that the as-sprayed coating was mainly composed of crystalline Yb₂Si₂O₇ with amorphous phase. The coating had a dense structure containing defects, such as pores, interfaces and microcracks. The TG-DTA results showed that there was almost no mass change from room temperature to 1200 °C, while a sharp exothermic peak appeared at around 1038 °C in DTA curve, which indicated that the amorphous phase crystallized. The thermal conductivity of the coating decreased with rise in temperature up to 600 °C and then followed by an increase at higher temperatures. The minimum value of the thermal conductivity of the Yb₂Si₂O₇ coating was about 0.68 W/(m K).     

Effects of Laser Remelting and Oxidation on NiCrAlY/8Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> Thermal Barrier Coatings

In this study, three groups of thermal barrier coatings (TBCs) samples were remelted by CO₂ laser with different laser energy densities (1, 5 and 10 J/mm²) to seal the surface of yttria-stabilized zirconia (YSZ) coatings. Microscopic observations showed that the cracks size and the remelted depth in YSZ coatings increased. A ~ 50-μm-thick dense layer was formed on the surface of YSZ coating in samples with 1 J/mm² energy density. Microindentation tests showed that the Vickers hardness of YSZ coatings increases with the increase in laser energy density. After isothermal oxidation at 1200 °C for 200 h, thinner thermally growth oxides were found in laser remelted YSZ samples under energy density of 1 J/mm² (6.32 ± 0.28 μm). Cyclic oxidation results showed that the weight gain per unit area of low energy density laser remelted TBCs was smaller than that of the high energy density laser remelted and as-sprayed TBCs.     

Fabrication and Properties of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> Composite Coatings

Al₂O₃ /xZrO₂ (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al₂O₃ and nano-sized monoclinic-ZrO₂ powders. Microstructural investigation showed that the coatings comprised well-separated Al₂O₃ and ZrO₂ lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al₂O₃ and tetragonal-ZrO₂ with trace of original α-Al₂O₃ and monoclinic-ZrO₂ phases. The effect of ZrO₂ addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO₂ improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.     

Processing and Mechanical Properties of Natural Rubber-ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanocomposites

We present preliminary results concerning natural rubber reinforced with nanometric ZnFe₂O₄ obtained from an industrial solid waste. The study investigate the influence of these nanometric ceramic particles on the processing as well as the mechanical properties of the obtained rubber composite, opening the possibility of partial replacement of carbon black and exposing a new potential composite material. The hardness of unfilled and reinforced rubber increased as nanometric ZnFe₂O₄ was increased. Besides, tensile properties of the reinforced rubber were measured, observing once again that as the amount of nanometric ZnFe₂O₄ particles was increased, ultimate strength improved from 2.5 MPa to almost 20 MPa.     

~ ~ 3＋ Sol-gel synthesis and photoluminescence characterization of La2Ti2O7.EU3＋nanocrystals

Eu³⁺ doped La₂Ti₂O₇ nanocrystals with pure monoclinic phase and size of about 100 nm were prepared by a citric acid (CA) assisted sol-gel method. Techniques of thermo-gravimetric (TG) and differential scanning calorimetry (DSC), X-ray diffraction (XRD), as well as transmission electron microscopy (TEM) were employed to characterize the as-synthesized nanoparticles. Furthermore, photoluminescence (PL) performances of the Eu³⁺ doped La₂Ti₂O₇ nanocrystals were evaluated with focus on the effects of calcination temperature and Eu³⁺ doping concentration on the photoluminescence properties.     

Effect of Microstructure on the Thermal Conductivity of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-YSZ Coatings

The microstructures of three atmospheric plasma-sprayed (APS) Al₂O₃-ZrO₂ coatings were investigated using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The differences in the microstructures of the three Al₂O₃-ZrO₂ coatings, including their phase compositions, cracks, pores, grain sizes, and solid solutions, were analyzed in detail. A close relationship was observed between the thermal conductivities of the coatings and the microstructures, and the Al₂O₃-YSZ coatings with more spherical pores, fewer vertical cracks, and finer grains exhibited the lowest thermal conductivity of 0.91 W/m·K. Compared with YSZ coatings, Al₂O₃-YSZ coatings can exhibit lower thermal conductivity, which may be attributed to the formation of an amorphous phase, smaller grains, and Al₂O₃-YSZ solid solution.     

Formation of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Diffusion Barrier Between Cr-Contained Stainless Steel and Cold-Sprayed Ni Coatings at High Temperature

A novel approach to prepare a coating system containing an in situ grown Cr₂O₃ diffusion barrier between a nickel top layer and 310SS was reported. Cold spraying was employed to deposit Ni(O) interlayer and top nickel coating on the Cr-contained stainless steel substrate. Ni(O) feedstock was prepared by mechanical alloying of pure nickel powders in ambient atmosphere, acting as an oxygen provider. The post-spray annealing was adopted to grow in situ Cr₂O₃ layer between the substrate and nickel coating. The results revealed that the diffusible oxygen can be introduced into nickel powders by mechanical alloying. The oxygen content increases to 3.25 wt.% with the increase of the ball milling duration to 8 h, while Ni(O) powders maintain a single phase of Ni. By annealing the sample in Ar atmosphere at 900 °C, a continuous Cr₂O₃ layer of 1-2 μm thick at the interface between 310SS and cold-sprayed Ni coating is formed. The diffusion barrier effect evaluation by thermal exposure at 750 °C shows that the Cr₂O₃ oxide layer effectively suppresses the outward diffusion of Fe and Cr in the substrate effectively.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Content on Electrical Breakdown Properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Cu Composite

Al₂O₃/Cu composites were prepared by external addition of Al₂O₃, and the effect of Al₂O₃ content on microstructure, density, hardness, electrical conductivity and vacuum electrical breakdown properties was studied. The results show that with increasing Al₂O₃ addition, the density of Al₂O₃/Cu composite significantly decreases, the hardness sharply increases and then slowly decreases, but the electrical conductivity invariably decreases. The vacuum breakdown test shows that with increasing Al₂O₃ addition, the breakdown strength first sharply increases and then decreases when the Al₂O₃ content exceeds 1.2 wt.%; the chopping current always exhibits a decreasing trend and the arc life first increases and then decreases. According to the morphology of arc erosion and analysis, the arc erosion resistance increases and then decreases sharply. In the range of experiments, the optimal arc erosion resistance of Al₂O₃/Cu composite can be obtained with the addition of 1.2 wt.% Al₂O₃.     

Influence of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Particle Size on Microstructure,Mechanical Properties and Abrasive Wear Behavior of Flame-Sprayed and Remelted NiCrBSi Coatings

The influence of micrometric alumina (low surface area-to-volume ratio) and nanometric alumina (high surface area-to-volume ratio) on microstructure, hardness and abrasive wear of a NiCrBSi hardfacing alloy coating applied to an AISI 304 substrate using flame spraying (FS) combined with surface flame melting (SFM) is studied. Remelting after spraying improved the mechanical and tribological properties of the coatings. Microstructural characterization using XRD, SEM and EDS indicated that alumina additions produced similar phases (NiSi, Ni₃B, CrC and Ni₃₁Si₁₂) regardless of the alumina size, but the phases differed in morphology, size distribution and relative proportions from one coating to another. The addition of 12 wt.% nanometric Al₂O₃ increased the phases concentration more than five- to sixfold and reduced the hard phases size about four-to threefold compared with NiCrBSi + 12 wt.% micrometric Al₂O₃. Nanoalumina led to reduced mass loss during abrasive wear compared to micrometric alumina and greater improvement in hardness.     

Thermal and structural role of additives in P<Subscript>2</Subscript>O<Subscript>5</Subscript>-ZnO-Sb<Subscript>2</Subscript>O<Subscript>3</Subscript> glass for low expansion sealing materials

A glass based on the P₂O₅-ZnO-Sb₂O₃ ternary system was modified with various additives, such as RO (R=Ca, Ba and Mn), B₂O₃ and V₂O₅, for low temperature and low expansion sealing materials. The glass transition temperature (T_g) and coefficient of thermal expansion (CTE) were monitored and reduced with additive compositions of RO. Additional incorporation of B₂O₃ at the expense of RO also showed a similar result. Significant improvement was observed when the glass was modified with V₂O_5. A glass showing T_g<350 °C along with CTE<65×10⁻⁷/°C was found, suggesting a high potential for low temperature sealing materials especially for display applications. The role of the quaternary element within the glass is discussed, along with the structural effect using Raman spectroscopy.     

Up-Date of a Thermodynamic Database of the ZrO<Subscript>2</Subscript>-Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System for TBC Applications

The thermodynamic database of the ZrO₂-Gd₂O₃-Y₂O₃-Al₂O₃ system is up-dated taking into account new data on lattice stabilities of ZrO₂, Gd₂O₃ and Y₂O₃ and heat capacity measurements for the monoclinic phase Gd₄Al₂O₉ and phase with garnet structure Gd₃Al₅O₁₂. New data for the heat capacities of Gd₂Zr₂O₇ (pyrochlore) and GdAlO₃ (perovskite) as well as on the enthalpy of formation of fluorite solid solutions (Zr_1−x Gd _x )O_2−x/2 were found to be in good agreement with calculated results. In comparison with the previous assessment, taking into account new experimental data resulted in a change of the melting character of the Gd₄Al₂O₉ phase from a peritectic one to a congruent one in the Gd₂O₃-Al₂O₃ system. Correspondently, in the ternary system ZrO₂-Gd₂O₃-Al₂O₃, the melting character of the three-phase assemblage Gd₂O₃ (B), Gd₄Al₂O₉ and GdAlO₃ changed from eutectic to transition type U. The T ₀-lines for T/M and F/T diffusionless transformations and driving force of partitioning to equilibrium assemblage T + F were calculated in the ZrO₂-Gd₂O₃-Y₂O₃ system.     

Mechanical alloying characteristic and thermal stability of Al<Subscript>78</Subscript>Fe<Subscript>20</Subscript>Zr<Subscript>2</Subscript> amorphous powders

The powders of pure Al, Fe, and Zr for preparing Al₇₈Fe₂₀Zr₂ were subject to a high-energy planetary ball milling. The microstructure evolution of the mixtures at the different intervals of milling was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). It was found that a nearly complete amorphization could be achieved in the mixtures after ball milling for 23 h. Further ball milling led to the crystallization of the amorphous powders. A long time ball milling, e.g., 160 h, led to a complete crystallization of the amorphous powders and the formation of Al₃Zr and Al1₃Fe₄. The crystallization products caused by ball milling are almost the same as that produced by isothermal annealing of the amorphous powders in vacuum at 800 K for 1 h.