Improved properties of scandia and yttria co-doped zirconia as a potential thermal barrier material for high temperature applications

Due to the limited temperature capability of current YSZ thermal barrier coating (TBC) material, considerable effort has been expended world-wide to research new candidates for TBC applications above 1200?°C. Our study suggested that Sc₂O₃ and Y₂O₃ co-doped ZrO₂ (ScYSZ) had excellent t’ phase stability even after annealed at 1500?°C for 336?h. The thermal expansion coefficient of ScYSZ was comparable to the value of YSZ. The thermal conductivity of fully dense ScYSZ was in the range of 2.13–1.91?W?m^?1?K^?1 (25–1300?°C), approximately 25% lower than that of YSZ. Although the fracture toughness of dense ScYSZ was slightly lower than YSZ, an evident decline in elastic modulus was found. Additionally, thermal cycling lifetime of plasma sprayed ScYSZ coating (914 cycles) at 1300?°C was about 2.6 times longer than its YSZ counterpart. The superior comprehensive properties confirm that ScYSZ is a prospective candidate material for high-temperature TBC application.     

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.     

Thermal cycling failure of the multilayer thermal barrier coatings based on LaMgAl11O19/YSZ

Thermal cycling failure of three multilayer TBCs based on LaMgAl₁₁O₁₉ (LaMA)/YSZ was comparatively investigated by using the burner-rig testing method in this work. Results indicate that through optimizing the weight ratio and thickness of the intermediate LaMA/YSZ composite layers, a five-layer TBC with much improved thermal cycling life of 11,749 cycles at 1372 °C surface and 1042 °C bond coat testing temperature has been realized. While, thermal cycling lifetimes of the tri- and six-layer TBCs were 7439 and 7804 cycles at surface/bond coat testing temperatures of 1378 °C/1065 °C and 1367 °C/1056 °C, respectively. Factors related to the 60 wt.% LaMA + 40 wt.% YSZ (60LaMA + 40YSZ) intermediate composite layer with the highest thermal expansion coefficient than other composite layers generating higher internal stress level to the tri- and six-layer TBCs, different bond coat temperature and TGO growth, as well as long-term stability of the LaMA coating during thermal cycling tests, were characterized and compared to understand the different thermal cycling lifetime and failure modes among such three multilayer TBCs.     

Interface design in 3D-SiC/Al-Si-Mg interpenetrating composite fabricated by pressureless infiltration

3D-SiC/Al-Si-Mg interpenetrating composites (IPCs) were fabricated by pressureless infiltration method. Interfaces in the 3D-SiC/Al-Si-Mg IPCs were modificated by using two different kinds of aluminum alloy Al-15Si-10Mg and Al-9Si-6Mg to infiltrate into 3D-SiC performs and different treated 3D-SiC preforms unoxidized or preoxidized in air at 1000?°C, 1100?°C and 1200?°C for 2?h respectively. Results showed that desired interfaces can be achieved in both IPCs made with those two aluminum alloys, as demonstrated by their excellent comprehensive properties. When the Al-15Si-10Mg alloy with excessive Si content is used for infiltration, interfaces in 3D-SiC/Al-Si-Mg IPC fabricated with the unoxidized 3D-SiC preform are directly bonded through atomic matching without any interfacial reaction and the composite has the properties of a thermal conductivity (TC) of 224.5?W/(m?°C), a thermal expansion coefficient (CTE) (RT ~ 300?°C) of 7.04?×?10^?6/°C and a bending strength (BS) of 277?MPa. When the Al-9Si-6Mg alloy with a lower Si content is used for infiltration, interface zone with a thickness around 200?nm forms in the 3D-SiC/Al-Si-Mg IPC fabricated with the 3D-SiC preform preoxidized at 1000?°C. The reaction-bonded interface is composed of AlN and MgAl₂O₄ which have better interface affinity with SiC and can isolate SiC effectively from liquid Al against the formation of detrimental Al₄C₃ phase. The composite has the properties of a TC of 219.5?W/(m °C), a CTE (RT ~ 300?°C) of 7.66?×?10^?6/°C and a BS of 318?MPa.     

The improvement in thermal and mechanical properties of TiB2 modified adhesive through the polymer-derived-ceramic route

An air stable high temperature adhesive synthesized via the polymer-derived-ceramic route had received increased attention in the last two decades. To improve the thermal stability and adhesion strength of a polysilazane (PSNB) adhesive, TiB₂ was added as active filler to join SiC ceramic discs. The thermal stability, phase composition and microstructure were investigated by using TGA, XRD, FT-IR, BSE and SEM measurements. Effects of the pyrolysis temperature and active filler TiB₂ on the microstructure and adhesion strength have been investigated. After curing and heat-treating at 120?°C and 1000?°C in air for 2?h, respectively, the adhesion strength of the modified adhesive reached up to 10.07?MPa (3 times higher than that of pure PSNB) at room temperature, and, more importantly, retained a strength of 8.0?MPa at 800?°C in air. It should be noted that the formation of a glass comprised of SiO₂-B₂O₃-TiO₂ and the emergence of the hexagonal and granular TiB₂ in the adhesive layer are mainly responsible for the enhanced high temperature strength.     

Thermogravimetric and differential thermal analysis of cellulose,hemicellulose, and lignin

The thermal degradation of samples of cellulose, hemicellulose, and lignin have been investigated using the techniques of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) between room temperature and 600°C. The results calculated from static and dynamic TGA indicated that the activation energy E for thermal degradation for different cellulosic, hemicellulose, and lignin samples is in the range 36–60, 15–26, and 13–19 kcal/mole, respectively. DTA of all the wood components studied showed an endothermic tendency around 100°C in an atmosphere of flowing nitrogen and stationary air. However, in the presence of flowing oxygen this endothermic effect was absent. In the active pyrolysis temperature range in flowing nitrogen and stationary air atmospheres, thermal degradation of Avicel cellulose occurred via a sharp endothermic and a sharp exothermic process, the endothermic nadir and exothermic peak being at 320° and 360°C, respectively. In the presence of oxygen, combustion of Avicel cellulose occurred via two sharp exothermic processes. DTA studies of different cellulose samples in the presence of air showed that the shape of the curve depends on the sources from which the samples were prepared as well as on the presence of noncellulosic impurities. Potassium xylan recorded a sharp exothermic peak at 290°C in a nitrogen atmosphere, and in a stationary air atmosphere it yielded an additional peak at 410°C, while in the presence of oxygen the curve showed two sharp exothermic peaks. DTA traces of periodate lignin in flowing nitrogen and air were the same and showed two exothermic peaks at 320° and 410°C, while in the presence of oxygen there were two exothermic peaks in the temperature range 200°–500°C.     

Thermal diffusivity characterization of europium zirconate,cerate and hafnate

The following paper presents study on synthesis and thermal diffusivity of europium zirconate, cerate and hafnate as a new types of materials with pyrochlore or fluorite type of lattice, dedicated to replacement of conventional 8YSZ (yttria stabilized zirconia) in TBC (thermal barrier coatings) systems for aircraft gas turbines.All materials were synthesized via solid-state reaction (SSR) preceded preparation of powder mixtures (mechanical milling in ethanol). The feedstock powders were characterized by analysis of crystallite size, particle size distribution and phase composition. On the base of DSC measurements, the parameters of high temperature sintering were selected (1350?°C/2?h/15?MPa). Structural characterization of obtained materials inclusive analysis of morphology, chemical and phase composition of sinters was performed. Thermal diffusivity was measured in temperature range 25÷1400?°C by laser flash analysis (LFA). The obtained materials with pyrochlore and fluorite type of lattice exhibit lower thermal diffusivity compared to that of yttria-stabilized zirconia at high temperatures. In particular, the most promising material in view of insulating properties is Eu₂Ce₂O₇, which exhibit much lower thermal diffusivity than Eu₂Zr₂O₇ and Eu₂Hf₂O₇, especially at temperature higher than 1000?°C. However, in temperature range 25–700?°C, europium hafnate and zirconate exhibit lower thermal diffusivity compared to that of europium cerate and 8YSZ.     

Thermal conductivity and stability of Al-doped ZnO nanostructured ceramics

Pure and Al-doped ZnO powders have been sintered by Spark Plasma Sintering. Al doping allows the ceramics to reach a relative density greater than 90% at a sintering temperature of 500?°C. The morphology of powder nanoparticles impacts the final grain size of the sintered bulk compounds. A ceramic sintered from isotropic nanoparticles of 30?nm in diameter can reach an average grain size of 110?nm, whereas a ceramic sintered from platelets and isotropic nanoparticles exhibits an average grain size in the submicrometric range. The influence of ceramic grain size on the thermal conductivity has been investigated. It shows that substantial decrease of the grain size from several microns down to 100?nm reduces the thermal conductivity from 29.5 to 7.8?W/m?K at 100?°C. The stability of nanostructured ceramic has also been checked. After SPS, an annealing at 500?°C in air also leads to grain growth.     

Nanomechanical behavior of yttria stabilized zirconia (YSZ) based thermal barrier coating

In the present study, the detailed evaluation of nanomechanical properties in terms of hardness and Young׳s modulus of duplex and compositionally graded YSZ based thermal barrier coating (TBC) have been evaluated by nanoindentation technique. Duplex and compositionally graded TBCs have been fabricated by thermal spray deposition technique. As TBCs are commonly applied for high temperature protection, effect of isothermal treatment in air (at 900 °C and 1000 °C) on nanomechanical properties has also been evaluated. Finally, the mechanical properties have been correlated with characteristics of the coating. The hardness and Young׳s modulus of the TBCs are found to increase with increased duration of thermal exposure. Modulus of resilience and resistance to plastic deformation of the duplex and compositionally graded TBC have also been evaluated at room temperature and with thermal exposure and discussed in detail.     

Preparation of diamine-POSS/Ag hybrid microspheres and its application in epoxy resin

Carbon nanowires having different functionality has been synthesized through the template assisted approach using poly(vinyl alcohol) (PVA) as precursor polymer at 400?°C, 600?°C, 700?°C and 800?°C in the absence of any catalyst. Carbon nanowires with a diameter range of about 90?C120?nm have been obtained. Scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy are been adopted to characterize the morphology, thermal properties and chemical configuration of the synthesized samples. Raman spectroscopy indicates carbonization of the samples upto 600?°C. Above that carbon-cluster formation is observed at 700?°C and 800?°C. SEM images show the formation of nanowires in alumite template by infiltration of PVA into the pores at 400?°C. The nanowires produced are very flexible at about 700?°C, above which the nanowires tended to retain their rigidity due to the formation of graphite clusters / crystallites.     

Hot corrosion behavior of BaLa2Ti3O10 exposed to calcium-magnesium-alumina-silicate at elevated temperatures

Calcium-magnesium-alumina-silicate (CMAS) attack has been regarded as one of the significant failure mechanisms for thermal barrier coatings (TBCs). In this study, CMAS corrosion behavior of BaLa₂Ti₃O₁₀, a novel TBC material, is investigated at 1300?°C and 1350?°C for 0.5?h, 4?h, 12?h and 24?h. Results reveal that BaLa₂Ti₃O₁₀ has high resistance to molten CMAS infiltration, attributable to the formation of a dense reaction layer. X-ray diffraction, scanning electron microscope, energy dispersive spectroscope, transmission electron microscope confirm that the layer consists of apatite, celsian and perovskite phases. With increased corrosion duration, the layer retains good phase stability and the thickness increases. The formation of corrosion products and the reaction layer are discussed according to a dissolution-reprecipitation mechanism and the optical basicity theory.     

Phase stability,thermo-physical properties and thermal cycling behavior of plasma-sprayed CTZ,CTZ/YSZ thermal barrier coatings

ZrO₂ co-stabilized by CeO₂ and TiO₂ with stable, nontransformable tetragonal phase has attracted much attention as a potential material for thermal barrier coatings (TBCs) applied at temperatures >?1200?°C. In this study, ZrO₂ co-stabilized by 15?mol% CeO₂ and 5?mol% TiO₂ (CTZ) and CTZ/YSZ (zirconia stabilized by 7.4?wt% Y₂O₃) double-ceramic-layer TBCs were respectively deposited by atmospheric plasma spraying. The microstructures, phase stability and thermo-physical properties of the CTZ coating were examined using scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric-differential scanning calorimeter (TG-DSC), laser pulses and dilatometry. Results showed that the CTZ coating with single tetragonal phase was more stable than the YSZ coating during isothermal heat-treatment at 1300?°C. The CTZ coating had a lower thermal conductivity than that of YSZ coating, decreasing from 0.89?W?m^?1 K^?1 to 0.76?W?m^?1 K^?1 with increasing temperature from room temperature to 1000?°C. The thermal expansion coefficients were in the range of 8.98?×?10^?6 K^?1 – 9.88 ×10^?6 K^?1. Samples were also thermally cycled at 1000?°C and 1100?°C. Failure of the TBCs was mainly a result of the thermal expansion mismatch between CTZ coating and superallloy substrate, the severe coating sintering and the reduction-oxidation of cerium oxide. The thermal durability of the TBCs at 1000?°C can be effectively enhanced by using a YSZ buffer layer, while the thermal cycling life of CTZ/YSZ double-ceramic-layer TBCs at 1100?°C was still unsatisfying. The thermal shock resistance of the CTZ coating should be improved; otherwise the promising properties of CTZ could not be transferred to a well-functioning coating.     

Morphological and thermal characterization of zirconia/hydroxyapatite composites prepared via sol-gel for biomedical applications

The thermal behavior of pure ZrO₂ and hydroxyapatite (denoted as Z and HAp, respectively), as well as three composites with different content of Z and HAp (Z90HAp10, Z70HAp30 and Z50HAp50) prepared via sol-gel method has been studied by thermogravimetry (TG) and first-order derivative of TG up to 1200?°C under inert gas atmosphere. Dehydration, loss of alcohol and acetylacetone and a multi-step thermal decomposition processes has been identified by analyzing the gases evolved in each step by Fourier transform infrared spectroscopy (FTIR). Fresh samples of Z-rich composites undergo an abrupt ejection of material from the crucible around 200?°C with noticeable increase of the sample temperature. During the occurrence of this phenomenon FTIR spectra demonstrated the evolution of gases (CO, CO₂, acetone and ethylene) due to the simultaneous decomposition of acetylacetone and ethanol, not present in the samples calcined at 120?°C. As far as the structural study is concerned, pure Z crystallizes at 1000?°C in the monoclinic system, but the presence of HAp in the composite materials enables the crystallization of Z in the tetragonal phase. Finally, the amorphization degree increases with increasing the content of Z in all the composites treated at 600 and 1000?°C.     

Processing and thermal properties of composites based on recycled PET,sisal fibers,and renewable plasticizers

This investigation focuses on the preparation of bio‐based composites from recycled poly (ethylene terephthalate) (PET) and sisal fibers (3 cm, 15 wt %), via thermopressing process. Plasticizers derived from renewable raw materials are used, namely, glycerol, tributyl citrate (TBC) and castor oil (CO), to decrease the melting point of the recycled PET (T_m ∼ 265°C), which is sufficiently high to initiate the thermal decomposition of the lignocellulosic fiber. All used materials are characterized by thermogravimetric analysis and differential scanning calorimetry, and the composites are also characterized via dynamic mechanical thermal analysis. The storage modulus (30°C) and the tan δ peak values of CT [PET/sisal/TBC] indicate that TBC also acts as a compatibilizing agent at the interface fiber/PET, as well as a plasticizer. To compare different processing methods, rheometry/thermopressing and compression molding are used to prepare the recycled PET/sisal/glycerol/CO composites. These two different methods of processing show no significant influence on the thermal properties of these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40386.     

Thermal shock resistance of Al2O3/SiO2 composites by sol-gel

In this paper, the SiO₂ ceramic matrix composites were reinforced by the two-dimensional (2D) braided Al₂O₃ fibers by sol-gel. To develop the high performance aeroengine with excellent resistance to thermal shock for advanced aerospace application, two different thermal shock temperatures (1100?°C and 1300?°C) and three different thermal shock cycles (10, 20 and 30 cycles) were tested and compared in this paper; besides, the thermal shock resistance of Al₂O₃/SiO₂ composites was investigated in air. Our results suggested that, the flexural strength of the untreated composites was 78.157?MPa, while the residual strength of Al₂O₃/SiO₂ composites under diverse thermal shock cycles and temperatures had accounted for about 95% and 50% of the untreated composites, respectively. Meanwhile, the density and porosity of the composites were gradually increased with the increase in test temperature. Moreover, the changes in fracture morphology and micro-structural evolution of the composites were also observed. Our observations indicated that, the fracture morphology of the composites mainly exhibited ductile fracture at the thermal shock temperature of 1100?°C, whereas brittle fracture at the thermal shock temperature of 1300?°C. Additionally, Al₂O₃/SiO₂ composites belonged to the Oxide/Oxide CMCs, so no new phase was formed after thermal shock tests. Above all, findings of this paper showed that Al₂O₃/SiO₂ composites had displayed outstanding thermal shock resistance.     

The Accelerating Effect of CaSO4 Within CMAS (CaO–MgO–Al2O3–SiO2) and Its Effect on the Infiltration Behavior in EB‐PVD 7YSZ

Infiltration and deposition of CaSO₄ in thermal barrier coatings (TBC) in addition to the CMAS deposits was found in many occasions on real aviation engines. The source and role of CaSO₄ on the degradation of TBC is not well understood. CaSO₄ containing CMAS was synthesized and a systematic study of its role on the CMAS infiltration behavior in EB‐PVD 7YSZ is presented in this work. Its influence on the melting and crystallization behavior of CMAS was studied with the help of differential scanning calorimetry. The decomposition of CaSO₄ into CaO and SO₃ was observed at 1050°C in laboratory air under the presence of CMAS using mass spectroscopy and in situ high‐temperature XRD. The same amount of CaO is brought into the CMAS system by means of adding CaCO₃, which will eventually decompose into CaO and CO₂ at 700°C. CMAS infiltration tests were carried out at different temperatures with and without CaSO₄/CaCO₃ and the results demonstrate that the sulfur has no direct effect on the aggressiveness of the anhydrite containing CMAS with regard to its infiltration behavior in EB‐PVD 7YSZ at high temperatures. The extra amount of calcia added to CMAS that is introduced by the evaporating species is responsible for enhanced infiltration of the deposits into the TBC.     

Exactly alternating silarylene—siloxane polymers: 6. Thermal stability and degradation behaviour

The thermal stability and degradation behaviour of a series of twelve different exactly alternating silarylene—siloxane polymers were investigated by several different methods including thermal gravimetric analysis (t.g.a.) in air and in nitrogen, long term (up to 48 h) high temperature (600° and 900°C) isothermal degradation in nitrogen, and rapid pyrolysis in helium. No weight loss was observed by t.g.a. until about 400°C, and two distinctly different mechanisms were observed, one for degradation in nitrogen (a single step process), and the other in air (a three step process). Under nitrogen, black, insoluble, carbon-hydrogen-silicon containing degradation products were obtained, which were stable in pure oxygen to at least 1100°C. In air, pure SiO₂ was obtained after heating to above 730°C. Isothermal investigations revealed that at temperatures of 600°C and above, weight loss by thermal degradation under a nitrogen atmosphere was completed in less than an hour, and the polymeric products which remained thereafter did not change any further even after 48 h at 900°C.     

Thermal conductivity of single- and multi-phase compositions in the ZrO2–Y2O3–Ta2O5 system

Compositions in the ZrO₂–Y₂O₃–Ta₂O₅ system are of interest as low thermal conductivity, fracture resistant oxides for the next generation thermal barrier coatings (TBC). Multiple phases occur in the system offering the opportunity to compare the thermal properties of single, two-phase, and three-phase materials. Despite rather large variations in compositions almost all the solid solution compounds had rather similar thermal conductivities and, furthermore, exhibited only relatively small variations with temperature up to 1000 °C. These characteristics are attributed to the extensive mass disorder in all the compounds and, in turn, small interfacial Kapitza (thermal) resistances. More complicated behavior, associated with the transformation from the tetragonal to monoclinic phase, occurs on long-term annealing in air of some of the compositions. However, the phases in two of the compositional regions do not change with annealing in air and their thermal conductivities remain unchanged suggesting they may be suitable for further exploration as thermally stable TBC overcoats.     

Thermal conductivity of air plasma sprayed yttrium heavily-doped lanthanum zirconate thermal barrier coatings

The yttrium heavily doped La₂Zr₂O₇ solid solutions coatings, with a Y to La molar ratio of 1:1, have been successfully prepared by air plasma spraying technique. The evolution of phase composition, phase structure and thermal conductivity of such coatings with annealing at 1300?°C has been investigated. The results show that, a single pyrochlore structure can be retained for coating after annealing up to 48?h, beyond which the fluorite phase begins to precipitate out. By comparing thermal conductivities to those undoped counterparts at a similar porosity level, we find a considerably flat thermal conductivity versus temperature (k-T) curve, suggesting the existence of a strong phonon scattering source, which is inferred as rattlers. In addition, after the segmentation of the fluorite phase, the thermal conductivity of corresponding coatings rises considerably, indicating that the fluorite phase has a higher thermal conductivity than that of pyrochlore phase. Moreover, while the as-sprayed coatings show a clear indication of radiative thermal conduction beyond 1000?°C, the thermal conductivity of annealed coatings do not show such an uprising trend after 1000?°C, suggesting that the radiative thermal conduction has been greatly suppressed. The reason is proposed as the formation of local dipoles due to local enrichment of certain elements influences the propagation of electromagnetic waves and thus suppresses the radiative thermal conduction.     

Experimental investigation of Al2O3/8YSZ and CeO2/8YSZ plasma sprayed thermal barrier coating on diesel engine

In this research work, aluminium oxide/yttria stabilized zirconia (20%Al₂O₃/80%8YSZ) and ceria/yttria stabilized zirconia (20%CeO₂/80%8YSZ) were coated through atmospheric plasma spray technique (APS) as thermal barrier coating (TBC) over CoNiCrAlY bond coat on aluminium alloy (Al-13%Si) substrate piston crown material and their thermal cycling behavior were studied experimentally. Thermal cycle test of both samples were conducted at 800?°C. Microstructural, phase and elemental analysis of the TBC coatings were experimentally investigated. The performance, combustion and emission characteristics of Al₂O₃/8YSZ, CeO₂/8YSZ TBC coated and uncoated standard diesel engine were experimentally investigated. The test results revealed that CeO₂/8YSZ based TBC has an excellent thermal cycling behavior in comparison to the Al₂O₃/8YSZ based TBC. The spallation of the Al₂O₃/8YSZ TBC occurred mainly due to the formation of thermally grown oxide (TGO), and growth of residual stresses at top coating and bond coating interface. The experimental results also revealed that the increase of brake thermal efficiency and reduction of specific fuel consumption for both TBC coated engine. Further reduction of HC, CO and smoke and increase of NOx emission were recorded for both TBC coated engine compared to the standard diesel engine.