Thermophysical behavior of thermal sprayed yttria stabilized zirconia based composite coatings

The effective thermal conductivity of a composite coating depends on intrinsic thermal conductivity of the constituent phases, its characteristics (size, shape) and volume fraction of porosities. The present study concerns studying the effect of CoNiCrAlY and Al₂O₃ content on the coefficient of thermal expansion and thermal conductivity of the YSZ (YSZ-CoNiCrAlY and YSZ-Al₂O₃) based composite coatings developed by thermal spray deposition technique. The coefficient of thermal expansion and thermal conductivity of the composite coatings were measured by push rod dilatometer and laser flash techniques, respectively, from room temperature to 1000 °C. Variation in density, porosity, coefficient of thermal expansion, and thermal conductivity was observed in the composite coatings with the addition of different volume fraction of CoNiCrAlY and Al₂O₃ powders in YSZ-CoNiCrAlY and YSZ-Al₂O₃ composites, respectively. Comparison between the theoretical and experimental thermal conductivities showed a mismatch varying from 4% to 58% for YSZ-CoNiCrAlY composite coatings and from 58% to 80% for YSZ-Al₂O₃ composite coatings. Model based analyses were used to understand the mechanism of thermal conductivity reduction in the composite coatings. It was concluded that the morphology of porosities varied with composition.     

Investigation of the thermal shrink mechanism,thermal conductivity and compressive resistance of TaTiP3O12 ceramics

Dense TaTiP₃O₁₂ ceramics were synthesized by the solid-state method and spark plasma sintering (SPS) with 6 wt% V₂O₅ as a sintering aid, and their phase, microstructure, thermal conductivity, hardness, compressive strength, and expansion property and mechanism were investigated. Results show that the pure phase can be achieved by the two methods. In particular, the sample prepared by SPS possesses a relative density of 97.62% and a porosity of 3.07%, and has better properties than that prepared by the solid-state method. The SPS sample has a thermal conductivity at room temperature of 2.03 w/(m· °C), a Vickers hardness of 4.34 GPa and a compressive strength of 175.98 MPa, which are 0.95, 1.49 and 1.59 times greater than those of the sample prepared by the solid-state method, respectively. In addition, the TaTiP₃O₁₂ ceramic prepared by SPS exhibits a linear ultralow negative thermal expansion property with a coefficient of thermal expansion of ?0.74 × 10^?6 °C ^?1 (-100–400 °C). The negative thermal expansion in TaTiP₃O₁₂ is induced by the coupling effect of [Ta(Ti)O₆] octahedron and [PO₄] tetrahedron caused by the transverse vibration of bridging oxygen atoms.     

Thermal properties of La2Zr2O7 double-layer thermal barrier coatings

La₂Zr₂O₇ is a promising thermal barrier coating (TBC) material. In this work, La₂Zr₂O₇ and 8YSZ-layered TBC systems were fabricated. Thermal properties such as thermal conductivity and coefficient of thermal expansion were investigated. Furnace heat treatment and jet engine thermal shock (JETS) tests were also conducted. The thermal conductivities of porous La₂Zr₂O₇ single-layer coatings are 0.50–0.66?W?m^?1?°C^?1 at the temperature range from 100 to 900°C, which are 30–40% lower than the 8YSZ coatings. The coefficients of thermal expansion of La₂Zr₂O₇ coatings are about 9–10?×?10^?6?°C^?1 at the temperature range from 200 to 1200°C, which are close to those of 8YSZ at low temperature range and about 10% lower than 8YSZ at high temperature range. Double-layer porous 8YSZ plus La₂Zr₂O₇ coatings show a better performance in thermal cycling experiments. It is likely because porous 8YSZ serves as a buffer layer to release stress.     

Influence of phase composition on microstructure and thermal properties of ytterbium silicate coatings deposited by atmospheric plasma spray

In this study, ytterbium silicate coatings with different compositions were designed by controlling the Yb₂O₃/ SiO₂ ratio and fabricated by atmospheric plasma spray. The microstructure and thermal properties of these coatings were characterized. Results showed that the Yb₂O₃-rich coatings contained Yb₂O₃ and Yb₂SiO₅ phases, which were characterized by Yb₂O₃ columnar grains, obvious interfaces between splats and many microcracks. The SiO₂-rich coatings were composed of Yb₂SiO₅ and Yb₂Si₂O₇ phases, which were composed of well bonded splats with many spherical pores. The Yb₂O₃-rich coatings had higher coefficient of thermal expansion values and lower thermal conductivities than the SiO₂-rich coatings. The SiO₂-rich coatings presented much better thermal cycling resistance than the Yb₂O₃-rich coatings. The relationship among phase composition, microstructure and thermal properties of ytterbium silicate coatings was analyzed. The results of this study may provide some clues for designs and applications of rare-earth silicates as environmental barrier coatings.     

Transparent glass and glass-ceramic in the binary system NaPO3-Ta2O5

Transparent and homogeneous tantalum phosphate glasses were prepared in the binary system (100-x)NaPO₃-xTa₂O₅ with x varying from 10 to 50 mol%. Thermal, structural, and optical properties, as well as crystallization mechanisms, were investigated by thermal analysis, X-ray diffraction, Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopies, optical absorption, transmission electron microscopy in terms of Ta₂O₅ content. FTIR and Raman results support the tantalum insertion in the phosphate chains with [TaO₆] polyhedra cross-linking the phosphate units. At higher Ta₂O₅ content, [TaO₆] clusters are formed and connected to the phosphate network by P-O-Ta bonds. This structural evolution is in good agreement with the thermal features measured by differential scanning calorimetry (DSC) with a strong increase of the T_g temperatures up to 920°C, high thermal stability against crystallization for low Ta₂O₅ content and increasing of crystallization tendency for the most Ta-concentrated samples. Besides, due to the progressive insertion of [TaO₆] units, the precipitation of Na₂Ta₈O₂₁ perovskite-like phase was identified in the sample with 50 mol% of Ta₂O₅. The optimal heat treatment conditions were identified using DSC measurements and a transparent glass-ceramic from 50NaPO₃ to 50Ta₂O₅ composition was prepared. The obtaines glass-ceramic has great potential for optical applications, such as host for rare-earth ions, nonlinear optical materials, and ferroelectric domain.     

Low leakage rate of silicate glass modified with Al2O3 for solid oxide fuel cell

The gas tightness of glass sealing materials is a big challenge for the solid oxide fuel cell (SOFC) stacks operating at high temperature. Thermal, sintering, crystallization behavior and gas tightness properties of the glass-based with two different Al₂O₃ contents sealants are evaluated and discussed. The study showed that the sealants avoid cracks at the interface on NiO-YSZ (NiO-yttria stabilized zirconia) and SUS430 stainless steel interconnect substrates. The Al₂O₃ embedded in the glass matrix as a second phase, and promoted crystallization of K[AlSi₃O₈] at the early stage. This may because some ultrafine Al₂O₃ particles whose structure is destroyed by prolonged high temperature treatment according XRD and TEM analysis. Especially, the sealant containing 5 wt% Al₂O₃ undergoes a thermal cycle and maintains a stable leakage rate below 10^?4 sccm?cm^?1 for about 1000 h at 750 °C. The above results prove the possibility of using the Al₂O₃-doped sealing glass for SOFC stacks.     

Understanding the structure,thermal, and optical properties in Al2O3-incorporated La2O3-TiO2-Nb2O5 glasses

Glasses in the 30La₂O₃-40TiO₂-30Nb₂O₅ system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La₂O₃-40TiO₂-(30−x) Nb₂O₅-xAl₂O₃ (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al₂O₃ on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al₂O₃ increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La₂O₃-40TiO₂-25Nb₂O₅-5Al₂O₃ (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO₄] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO₄] tetrahedral linkages to [TiO₅] and [NbO₆] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al₂O₃ substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La₂O₃-40TiO₂-30Nb₂O₅ (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.     

Thermal Expansion of Rare‐Earth Pyrosilicates

The use of RE₂Si₂O₇ materials as environmental barrier coatings (EBCs) and in the sintering process of advanced ceramics demands a precise knowledge of the coefficient of thermal expansion of the RE₂Si₂O₇. High‐temperature X‐ray diffraction (HTXRD) patterns were collected on different RE₂Si₂O₇ polymorphs, namely A, G, α, β, γ, and δ, to determine the changes in unit cell dimensions. RE₂Si₂O₇ compounds belonging to the same polymorph showed, qualitatively, very similar unit cell parameters behavior with temperature, whereas the different polymorphs of a given RE₂Si₂O₇ compound exhibited markedly different thermal expansion evolution. The isotropy of thermal expansion was demonstrated for the A‐RE₂Si₂O₇ polymorph while the rest of polymorphs exhibited an anisotropic unit cell expansion with the biggest expansion directed along the REO_x polyhedral chains. The apparent bulk thermal expansion coeficcients (ABCTE) were calculated from the unit cell volume expansion for each RE₂Si₂O₇ compound. All compounds belonging to the same polymorph exhibited similar ABCTE values. However, the ABCTE values differ significantly from one polymorph to the other. The highest ABCTE values correspond to A‐RE₂Si₂O₇ compounds, with an average of 12.1 × 10^?6 K^?1, whereas the lowest values are those of β‐ and γ‐RE₂Si₂O₇, which showed average ABCTE values of ~4.0 × 10^?6 K^?1.     

Preparation and properties of LaMgAl11O19 thermal barrier coatings doped with Gd2O3

As a rare earth hexaaluminate, LaMgAl₁₁O₁₉ (LMA) has been one of the most promising materials used as thermal barrier coatings (TBCs). A large amount of amorphous phase, however, often exists in the plasma-sprayed LMA coating and significantly reduces the service lifetime of TBCs. In this study, La_1-xGd_xMgAl₁₁O₁₉ (x = 0, 0.2, 0.4, 0.6, and 0.8) ceramic powders are synthesised by solid-state reaction, and all of these powders are employed to prepare the corresponding coatings. The phase compositions and microstructures of samples are examined by X-ray diffraction and scanning electron microscopy, respectively. The linear thermal expansion behaviour and thermal cycling behaviour of the coatings are also analysed. The results show that the amorphous phase content is decreased and the thermal expansion behaviour is improved by doping the coatings with Gd₂O₃. The thermal cycling lifetime of the coating, however, basically remains unchanged.     

New double-ceramic-layer thermal barrier coatings based on zirconia–rare earth composite oxides

A series of La₂O₃–ZrO₂–CeO₂ composite oxides were synthesized by solid-state reaction. The final product keeps fluorite structure when the molar ratio Ce/Zr ≥ 0.7/0.3, and below this ratio only mixtures of La₂Zr₂O₇ (pyrochlore) and La₂O₃–CeO₂ (fluorite) exist. Averagely speaking, the increase of CeO₂ content gives rise to the increase of thermal expansion coefficient and the reduction of thermal conductivity, but La₂(Zr_0.7Ce_0.3)₂O₇ has the lowest sintering ability and the lowest thermal conductivity which could be explained by the theory of phonon scattering. Based on the large thermal expansion coefficient of La₂Ce_3.25O_9.5, the low thermal conductivities and low sintering abilities of La₂Zr₂O₇ and La₂(Zr_0.7Ce_0.3)₂O₇, double-ceramic-layer thermal barrier coatings were prepared. The thermal cycling tests indicate that such a design can largely improve the thermal cycling lives of the coatings. Since no single material that has been studied so far satisfies all the requirements for high temperature thermal barrier coatings, double-ceramic-layer coating may be an important development direction of thermal barrier coatings.     

Thermal shock performance and failure behavior of Zr6Ta2O17-8YSZ double-ceramic-layer thermal barrier coatings prepared by atmospheric plasma spraying

Zr₆Ta₂O₁₇ has higher fracture toughness, better phase stability, thermal insulation performance and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (8 YSZ, 7–8 wt%) at temperatures above 1200 °C. However, the thermal expansion coefficients between Zr₆Ta₂O₁₇ coating and bond coating do not match well. A double-ceramic-layer design is applied to alleviate the thermal stress mismatch. The Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer thermal barrier coatings (TBCs) are prepared by atmospheric plasma spraying (APS). During the thermal shock test, Zr₆Ta₂O₁₇/8 YSZ double-ceramic-layer TBCs exhibit a better thermal shock resistance than 8 YSZ and Zr₆Ta₂O₁₇ single-layer TBCs. The thermal shock performance and failure mechanism of TBCs in the thermal shock test are investigated and discussed in detail.     

Tribological properties of selected ceramic coatings

The paper presents the characteristics of some ceramic coatings obtained by a plasma spray method. The ceramic coatings Al₂O₃, Cr₂O₃ and Cr₂O₃?+?5% TiO₂ were evaluated. Also the influence of the NiCr interlayer on the functional properties of sprayed coatings was studied. Other parameters studied included: thickness; microhardness; adhesion of the coatings; resistance to abrasive wear and thermal cyclic loading. The addition of TiO₂ to the Cr₂O₃ material increased the coating density, but did not substantially reduce the hardness. On the other hand, the lowest loss of material thickness was seen for Cr₂O₃; while the Al₂O₃ and the Cr₂O₃?+?5 wt.% TiO₂ material showed a higher loss. The loss in the case of the latter two was about the same. Relatively, higher values of abrasive wear resistance were observed in the Cr₂O₃ coatings, as compared to the reference material (Al₂O₃ coating), and the highest microhardness values were measured in the Cr₂O₃ coating. Finally, the metal interlayers in all coatings increased their resistance to thermal shock. All the coatings, using the interlayer to reduce differences in coefficients of thermal expansion, were suitable for the purpose of the thermal loading up to 1000?°C.     

Thermal expansion of specimens of niobium and tantalum pentoxides obtained by melting in an optical furnace

Thermal expansion of high-purity niobium and tantalum pentoxides is studied. It is shown that specimens of Nb₂O₅ and Ta₂O₅ obtained by melting in an optical furnace and subsequent rapid cooling in air to room temperature possess a domain of negative thermal expansion and hysteresis of the dependence of the elongation on the temperatures of heating and cooling. Since the volume of a test cell computed from data of x-ray measurement increases with growth in the temperature, the negative values of the elongation of specimens of melted Nb₂O₅ and Ta₂O₅ can be explained by merging of microcracks formed due to anisotropy of the thermal expansion when the ingots are cooled. When designing and fabricating ceramic articles with protective coatings from niobium and titanium pentoxides to be used at 1000°C, preference should be given to ceramics with low and even negative values of CLTE. __________ Translated from Novye Ogneupory, No. 4, pp. 38–43, April, 2007.     

Material-genome perspective towards tunable thermal expansion of rare-earth di-silicates

Optimization of thermal expansion coefficient (CTE) mismatch among constituent rare-earth silicate layers is a critical challenge for the optimal multilayer thermal/environmental barrier coating (T/EBC) architecture for SiC_f/SiC_m CMCs. In this study, thermal expansion properties for β-, γ- and δ-RE₂Si₂O₇ polymorphs are investigated via DFT calculations. The interaction between rare-earth (RE) atoms and neighboring bridging oxygen (O_B) atoms, as well as the structure of [O₃SiO_BSiO₃] pyrosilicate units are the characteristic “gene” that controls the positive or negative contribution from low-frequency vibration patterns to the overall phonon anharmonicity, and eventually determine the significantly different CTE of RE₂Si₂O₇ polymorphs. Inspired by the concept of “genome modification”, γ-(Dy_0.15Y_0.85)₂Si₂O₇ solid solution is designed and synthesized, which shows notable enhancements of CTE as compared with γ-Y₂Si₂O₇. Such tunable CTE could presumably be explained by doping-induced localized lattice distortion around [O₃SiO_BSiO₃] pyrosilicate units, leading to switchable magnitude of negative contribution from low-frequency phonons to thermal expansion.     

A novel disubstituted Lindqvist-type polyoxomolybdate [Te2Mo4O19] supporting two organic vanadyl moieties: Synthesis, characterization, and crystal structure of {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]}

The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)₂]₂(4,4-bipy)[Te₂Mo₄O₁₉]} has been synthesized hydrothermally and characterized by elemental analyses, XPS, IR, TG-DTA and X-ray single crystal diffraction. The structural analysis shows that the neutral molecular unit [V(2,2-bipy)₂]₂[Te₂Mo₄O₁₉] consists of a novel Lindqvist-type polyanion [Te₂Mo₄O₁₉]⁶⁻ supporting two vanadyl moieties [V(2,2-bipy)₂]³⁺, and such neutral molecules are joined together by π − π stacking interactions between the pyridine groups to form a two-dimensional grid-like network with non-coordinating “guest” 4,4-bipys encapsulated.     

Thermal performance regulation of high-entropy rare-earth disilicate for thermal environmental barrier coating materials

We prepared the novel high-entropy (xRE_1/x)₂Si₂O₇ (RE = Y, Yb, Er, Sc, Gd and Eu, x = 2–6) ceramics by a two-step method for the application of thermal environmental barrier coatings (TEBCs), and the effect of configuration entropy and lattice distortion on microstructures and thermal properties at high temperature were investigated. The results showed that the configuration entropy resulted from mass disorder can only contribute to the stability of thermal properties and microstructure. Lattice distortion should be responsible for reduction in thermal properties, which may be due to the enhancement of atomic nonharmonic vibration, resulting in intensified phonon scattering and hindering atomic amplitude oscillation. As-prepared high-entropy (Y_1/6Yb_1/6Er_1/6Sc_1/6Gd_1/6Eu_1/6)₂Si₂O₇ ceramic exhibited the relatively low thermal diffusivity, thermal conductivity and coefficient of thermal expansion, which were 0.89–0.50 mm² s^–1, 1.99–2.50 W m^–1 K^–1 and (3.01–3.78) × 10^–6 K^–1 in the temperature range of 293–1373 K, respectively. This work provides a solid guarantee for the application of TEBC materials.     

Structure and crystallization of ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Structure and crystalline behavior of the ternary system ZnO-B₂O₃-P₂O₅ glasses were investigated by means of X-ray diffraction (XRD) and infrared Raman spectra. The research showed that number of the planar [BO₃] units increases with the increase of B₂O₃ content. When the B₂O₃ content is above ≥10 mol %, the relative content of planar [BO₃] units increases rapidly and causes weakening of the glass structure and decrease in the chemical stability. In the crystallized glasses the predominant crystal phase Zn₂P₂O₇ decreases with the increase of B₂O₃ content, while the crystal phase BPO₄ increases with it, which cause the declining of chemical stability and the decrease of thermal coefficients of expansion.     

Transformations of the Crystal Structure in a Series of Rubidium Boroleucite Solid Solutions from the X-ray Powder Diffraction Data

The crystal structures of rubidium boroleucite RbBSi₂O₆ [a = 12.785(1) Å] and two silicon-rich solid solutions Rb_0.96(B_0.77Si_2.18)_2.95O₆ [a = 12.858(1) Å] and Rb_0.92(B_0.46Si_2.42)_2.88O₆ [a = 12.914(1) Å] are refined in the space group I4¯3d (KBSi₂O₆ structural type) by the Rietveld method. Polycrystalline samples are prepared through the crystallization of glasses. The substitution Si⁴⁺ B³⁺ in tetrahedra of the borosilicate framework occurs with the charge compensation due to a deficit of rubidium and boron. The formation of vacancies in tetrahedral positions leads to the breaking of bonds between tetrahedra, and bridging oxygen atoms become terminal atoms.     

Phase and microstructure evolution in plasma sprayed Yb2Si2O7 coatings

Yb₂Si₂O₇ coatings were deposited on Si/SiC substrates by atmospheric plasma spray (APS). The different power and plasma chemistries used in this work produced mainly amorphous crack-free coatings with compositions shifted to lower SiO₂ content with higher power and H₂ flow. Differences in microstructure and thermomechanical properties (crystallization behavior, thermal expansion coefficient and thermal conductivity) of as-deposited and thermally treated coatings were directly related to the evolution from amorphous to crystalline phases. A Yb₂SiO₅ metastable phase was identified after thermal treatments at temperatures ～ 1000 °C that transformed to its stable isomorph at 1220 °C. This transformation, followed by the growth of the crystal cell volume, promoted the coating expansion and the “healing” of microcracks present in the amorphous as-sprayed coating.     

Electrical Properties,Cation Distributions,and Thermal Expansion of Manganese Cobalt Chromite Spinel Oxides

As the oxidation and chromium volatilization of chromia‐forming alloy interconnects can cause Solid oxide fuel cells (SOFC) cathode poisoning and cell degradation, spinel coatings like Mn_1.5Co_1.5O₄ have been applied as a barrier to oxygen and chromium diffusion. To evaluate their long‐term stability, the properties of the reaction layer between the Mn_1.5Co_1.5O₄ coating and Cr₂O₃ scale formed on the alloy surface need to be characterized. Therefore, compositions of Mn_1.5?0.5xCo_1.5?0.5xCr_xO₄ (x = 0–2) were prepared to investigate their electrical properties, cation distributions, and thermal expansion behavior at high temperature. With increasing Cr content in manganese cobalt spinel oxides, the cubic crystal structure is stabilized and the electrical conductivity and coefficient of thermal expansion both decrease. The cation distributions determined from neutron diffraction show that Cr and Mn have stronger preference for octahedral sites in the spinel structure as compared with Co.