Self-crystallization characteristics of calcium-magnesium-alumina- silicate (CMAS) glass under simulated conditions for thermal barrier coating applications

Understanding self-crystallization characteristics of calcium-magnesium-alumina- silicate (CMAS) glass is of great significance for seeking for solution to its corrosion to thermal barrier coatings (TBCs). Here, we design a series of experiments to investigate the relationship between CMAS self-crystallization behavior and cooling/heating rates and dwell temperature, and emphasize the potential influence of self-crystallization on CMAS corrosion behavior to TBCs. With the cooling rate decreasing, crystalline phases formed in a sequence of diopside, wollastonite and anorthite, and the thickness of the crystalline layer increased. During the heating process, diopside and melilite phases formed when the temperature was lower than 1050 °C; while at higher temperatures, melilite transformed to anorthite and wollastonite, independent on the heating rate. Although self-crystallization can slow molten CMAS penetration, the function on protecting TBCs from damage is limited, and other strategies alleviating CMAS corrosion are necessitated to be developed.     

Crystallization behavior of CMAS and NaVO3+CMAS mixture and its potential effect to thermal barrier coatings corrosion

Calcium-magnesium-alumina-silicate (CMAS) and molten salt corrosion pose great threats to thermal barrier coatings (TBCs), and recently, a coupling effect of CMAS and molten salt has been found to cause even severer corrosion to TBCs. In this study, the crystallization behavior of CMAS and CMAS+NaVO₃ is investigated for potentially clarifying their corrosion mechanisms to TBCs. Results indicated that at 1000 °C and 1100 °C, CMAS was crystallized to form CaMgSi₂O₆, while at 1200 °C, the crystallization products were CaMgSi₂O₆, CaSiO₃ and CaAl₂Si₂O₈. The introduction of NaVO₃ in CMAS reduced the crystallization ability, and as the NaVO₃ content increased, glass crystallization occurred at a lower temperature, with crystallization products mainly consisting of CaAl₂Si₂O₈ and CaMgSi₂O₆. At 1200 °C, CMAS+10 wt% NaVO₃ was in a molten state without any crystallization, which suggested that NaVO₃ addition in CMAS could reduce its melting point, indicating enhanced penetration ability in TBCs and thus increased corrosiveness.     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.     

The mechanical and thermal properties,CMAS corrosion resistance,and the wettability of novel thermal barrier material GdTaO4

Because the CMAS corrosion and phase transformation at elevated temperatures above 1250 °C have limited the applications of traditional YSZ, the design of novel thermal barrier materials is a hotspot. GdTaO₄ is considered as a type of potential novel thermal barrier material owing to its low thermal conductivity. In this study, the mechanical and thermal properties, CMAS corrosion resistance, and the wettability of the GdTaO₄ were studied and compared with that of YSZ. The results show that the coefficient of thermal expansion and hardness of GdTaO₄ are 14.1 × 10⁻⁶ K⁻¹ (1350 °C) and 534.2 Hv_0.3 respectively. The thickness of CMAS reaction layer of GdTaO₄ is ~30.8 μm after 24 h reaction at 1350 °C, which is thinner than that of YSZ. After corrosion reaction, the CMAS glass aggregated instead of completely disappearing or continuously extending over the surface of GdTaO₄. The main reaction product is Ca₂Ta₂O₇, and the anorthite phase may not be detected, which is similar to YTaO₄. By comparison, the dense substrate of YSZ became porous and CMAS glass has disappeared after 10 h. CMAS corrosion at 1350 °C. The on-line contact angle results show that the wettability of CMAS on GdTaO₄ is worse than that on YSZ at 1350 °C, while the opposite of the work of adhesion, which indicates that GdTaO₄ can remove liquid CMAS more easily than YSZ TBCs during the service. Furthermore, the corrosion depth and areas of GdTaO₄ are smaller than those of YSZ in the same situation. These findings suggest that GdTaO₄ possesses better high-temperature properties and CMAS corrosion resistance than YSZ as a kind of potential of thermal barrier material.     

The effect of TiO2 additions on CaO–MgO–Al2O3–SiO2 (CMAS) crystallization behavior from the melt

Titania (TiO₂) was introduced into a model calcium-magnesium aluminosilicate (CMAS) glass in additions of 5-20 wt%. The crystallization behavior of the mixtures was characterized over a series of temperature profiles and compared to that of CMAS alone. X-ray diffraction, differential scanning calorimetry, light and scanning electron microscopy, and energy dispersive spectroscopy were used to characterize glass and crystalline products. Titania additions in the amount of approximately 12.5-20 wt% aided in the formation of CaTiO₃ from melts equilibrated at either 1300 or 1500°C and cooled at 10°C/min. Holding CMAS + TiO₂ (TiO₂ ≥ 10 wt%) at 900°C after cooling from 1300/1500°C resulted in the formation of additional crystalline phases including melilite, paqueite, and diopside. Implications for CMAS interactions with thermal and environmental barrier coatings are discussed.     

Preparation of nanostructured Gd2Zr2O7-LaPO4 thermal barrier coatings and their calcium-magnesium-alumina-silicate (CMAS) resistance

Nanostructured 30 mol% LaPO₄ doped Gd₂Zr₂O₇ (Gd₂Zr₂O₇-LaPO₄) thermal barrier coatings (TBCs) were produced by air plasma spraying (APS). The coatings consist of Gd₂Zr₂O₇ and LaPO₄ phases, with desirable chemical composition and obvious nanozones embedded in the coating microstructure. Calcium-magnesium-alumina- silicate (CMAS) corrosion tests were carried out at 1250 °C for 1–8 h to study the corrosion resistance of the coatings. Results indicated that the nanostructured Gd₂Zr₂O₇-LaPO₄ TBCs reveals high resistance to penetration by the CMAS melt. During corrosion tests, an impervious crystalline reaction layer consisting of Gd-La-P apatite, anorthite, spinel and tetragonal ZrO₂ phases forms on the coating surfaces. The layer is stable at high temperatures and has significant effect on preventing further infiltration of the molten CMAS into the coatings. Furthermore, the porous nanozones could gather the penetrated molten CMAS like as an absorbent, which benefits the CMAS resistance of the coatings.     

CaO–MgO–Al2O3–SiO2 (CMAS) corrosion behaviour of LaMgAl11O19/GdPO4 thermal barrier coating materials

CaO–MgO–Al₂O₃–SiO₂ (CMAS) corrosion poses serious hidden dangers for the application of thermal barrier coatings (TBCs). In this study, LaMgAl₁₁O₁₉ (LMA) and GdPO₄ were mixed at molar ratios of 2:1, 1:1 and 1:2 to prepare LMA/GdPO₄ materials, and the CMAS corrosion behaviours of these materials were investigated at 1300°C–1500 °C for 20 h and 40 h. It was demonstrated that temperature was the main factor influencing the corrosion behaviours and products. The materials were damaged at 1300 °C by the crystallization of CMAS melts to form CaAl₂Si₂O₈. In contrast, the materials were corroded by CMAS melts via the reaction between CMAS and GdPO₄ at 1500 °C. These results indicate that the addition of GdPO₄ to LMA can improve the resistance of the LMA material to CMAS corrosion.     

Enhanced calcium–magnesium–aluminosilicate (CMAS) resistance of GdAlO3 (GAP) for composite thermal barrier coatings

The impact of calcium–magnesium–alumino-silicate (CMAS) degradation is a critical factor for development of new thermal and environmental barrier coatings. Several methods of preventing damage have been explored in the literature, with formation of an infiltration inhibiting reaction layer generally given the most attention. Gd₂Zr₂O₇ (GZO) exemplifies this reaction with the rapid precipitation of apatite when in contact with CMAS. The present study compares the CMAS behavior of GZO to an alternative thermal barrier coating (TBC) material, GdAlO₃ (GAP), which possesses high temperature phase stability through its melting point as well as a significantly higher toughness compared with GZO. The UCSB laboratory CMAS (35CaO–10MgO–7Al₂O₃–48SiO₂) was utilized to explore equilibrium behavior with 50:50 mol% TBC:CMAS ratios at 1200, 1300, and 1400°C for various times. In addition, 8 and 35 mg/cm² CMAS surface exposures were performed at 1425°C on dense pellets of each material to evaluate the infiltration and reaction in a more dynamic test. In the equilibrium tests, it was found that GAP appears to dissolve slower than GZO while producing an equivalent or higher amount of pore blocking apatite. In addition, GAP induces the intrinsic crystallization of the CMAS into a gehlenite phase, due in part to the participation of the Al₂O₃ from GAP. In surface exposures, GAP experienced a substantially thinner reaction zone compared with GZO after 10 h (87 ± 10 vs. 138 ± 4 μm) and a lack of strong sensitivity to CMAS loading when tested at 35 mg/cm² after 10 h (85 ± 13 versus 246 ± 10 μm). The smaller reaction zone, loading agnostic behavior, and intrinsic crystallization of the glass suggest this material warrants further evaluation as a potential CMAS barrier and inclusion into composite TBCs.     

Production of ceramic pigments with diopside and anorthite structure using the gel method

The possibility of producing ceramic pigments with the diopside and anorthite structures by the sol-gel method using wollastonite is studied. It is established that the use of the gel method intensifies the synthesis of anorthite and diopside crystal structures by means of better homogenization of the batch components at the mixing stage. A positive factor is the effective formation of anorthite and diopside structures at relatively low temperatures (about 1100°C), as well as the mineralizing effect of the chromophores on the crystallization of these minerals. __________ Translated from Steklo i Keramika, No. 8, pp. 26–28, August, 2006.     

Effect of MgF2 addition on sinterability and mechanical properties of fluorapatite ceramic composites fabricated by wollastonite and phosphate glass

In this paper, we successfully report the design and synthesis of fluorapatite ceramic composites using phosphate glass and wollastonite as raw materials via a simple sintering method. The effects of MgF₂ additives in phase composition, microstructure, densification, and mechanical properties are investigated at various temperatures from 600 °C to 900 °C, and characterized by SEM/EDS, XRD, FTIR, linear shrinkage and water absorption, flexural strength analysis. It shows that the densification and mechanical behavior of composites increase with both the sintering temperature and MgF₂ content. Especially, the sample SCPF-7 exhibits the highest densification and optimal mechanical properties at 900 °C. At these conditions, the water absorption of fluorapatite ceramic composite is less than 0.20%, and the flexural strength is over 70 MPa. For the microstructure analysis, the formation of fluorapatite with a rod-like microstructure is enhanced with the increase of MgF₂ content. The amelioration of these properties is due to the formation of a new phase which helps to the formation of compact microstructure. The findings in this work provide a feasible strategy for the preparation of fluorapatite ceramic composites from available phosphate glass and wollastonite at a lower temperature.     

Plasma sprayed nanostructured GdPO4 thermal barrier coatings: Preparation microstructure and CMAS corrosion resistance

Nanostructured GdPO₄ thermal barrier coatings (TBCs) were prepared by air plasma spraying, and their phase structure evolution and microstructure variation due to calcium–magnesium–alumina–silicate (CMAS) attack have been investigated. The chemical composition of the coating is close to that of the agglomerated particles used for thermal spraying. Nanozones with porous structure are embedded in the coating microstructure, with a percentage of ~30%. CMAS corrosion tests indicated that nanostructured GdPO₄ coating is highly resistant to penetration by molten CMAS at 1250°C. Within 1 hour heat treatment duration, a continuous dense reaction layer forms on the coating surface, which are composed of P–Si apatite based on Ca_2+xGd_8?x(PO₄)_x(SiO₄)_6?xO₂, anorthite and spinel phases. This layer provides effective prevention against CMAS further infiltration into the coating. Prolonged heat treatment densifies the reaction layer but does not change its phase composition.     

The effect of boron containing frits on the anorthite formation temperature in kaolin–wollastonite mixtures

In order to investigate the effect of boron containing frits on anorthite formation temperature in kaolin–wollastonite mixture, four different frit compositions containing boron were prepared according to Seger formulas. One of these compositions also contained lead. Four different batches composed of 40 mass% kaolin, 40 mass% wollastonite and 20 mass% frit were prepared. The linear dilatometric (LD) curves of the batches were determined and subsequently the firing schedule (FS) curves were obtained from the LD curves. Cylindrical pellets prepared from each of the batches were fired in an especially designed furnace up to respectively 950, 975, 1000, 1025, 1050 °C. The firing period including the cooling process was adjusted to 210 min. The variation of the bulk densities of the products as a function of temperature were examined. X-ray diffraction (XRD) patterns of the products were also determined and it was observed that the minimum anorthite formation temperature was 1000 °C. Since it was known that with batches not containing any frit, the minimum anorthite formation temperature was 1100 °C, it was understood that leaded or unleaded boron containing frits decreased the anorthite formation temperatures around 100 °C.     

Firing transformations of Chilean clays for the manufacture of ceramic tile bodies

This contribution is focused on the study of the mineralogical changes occurring in the ceramic body after heating ceramic clays. Chile has an important local ceramic industry. Five deposits of clays with industrial applications were studied. The clays came from San Vicente de Tagua-Tagua (SVTT), Litueche (L), Las Compañías-Río Elqui (LC), La Herradura-Coquimbo (LH) and Monte Patria-Coquimbo (MP). The samples were heated to 830, 975, 1080 and 1160 °C keeping at the maximum temperature for 35 min. The bending strength of each ceramic body was determined at 1100 °C. Mineralogical analysis of the fired samples was carried out by X-ray diffraction. The SVTT contained quartz, spinel, cristobalite, microcline, albite, anorthite, hematite and enstatite; the LC clays quartz, mullite, spinel, microcline, albite, anorthite, hematite, diopside, enstatite, illite/muscovite and talc; the LH clays quartz, cristobalite, microcline, albite, anorthite, hematite, diopside, illite and augite; the MP clays quartz, cristobalite, microcline, albite, anorthite, hematite, diopside, gehlenite, enstatite and wollastonite and the L clays quartz, microcline and mullite. The persistence of illite at at least 900 °C was observed for LC and LH. SVTT and LH showed the required specifications for earthenware. The L clays were refractory clays with very low bending strength.     

Solution combustion synthesis of calcia-magnesia-aluminosilicate powder and its interaction with yttria-stabilized zirconia and co-doped yttria-stabilized zirconia

Thermal Barrier Coatings (TBCs) play a significant role in improving the efficiency of gas turbines by increasing their operating temperatures. The TBCs in advanced turbine engines are prone to silicate particles attack while operating at high temperatures. The silicate particles impinge on the hot TBC surfaces and melt to form calcia-magnesia-aluminosilicate (CMAS) glass deposits leading to coating premature failure. Fine powder of CMAS with the composition matching the desert sand has been synthesized by solution combustion technique. The present study also demonstrates the preparation of flowable yttria-stabilized zirconia (YSZ) and cluster paired YSZ (YSZ-Ln₂O₃, Ln = Dy and Gd) powders by single-step solution combustion technique. The as-synthesized powders have been plasma sprayed and the interaction of the free standing TBCs with CMAS at high-temperatures (1200 °C, 1270 °C and 1340 °C for 24 h) has been investigated. X-ray diffraction analysis of CMAS attacked TBCs revealed a reduction in phase transformation of tetragonal to monoclinic zirconia for YSZ-Ln₂O₃ (m-ZrO₂: 44%) coatings than YSZ (m-ZrO₂: 67%). The field emission scanning electron microscopic images show improved CMAS resistance for YSZ-Ln₂O₃ coatings than YSZ coatings.     

Effect of firing temperature and atmosphere on ceramics made of NW Peloponnese clay sediments. Part I: Reaction paths,crystalline phases,microstructure and colour

Archaeometric investigation on ancient ceramic collected from excavations in NW Peloponnese demonstrated that the ancient potters used the local Plio-Pleistocene clay sedimentary deposits for a large historical period. Three representative raw materials of these local sediments were chosen for experimental work aiming to evaluate their firing behaviour in a propane-fired kiln, with a different atmosphere and temperature. The determination of mineralogy and microstructure was carried out by XRD and SEM-EDS analysis. For ceramics fired at 850 and 950 °C, no significant mineralogical and microstructural differences were observed between the oxidising and reducing atmosphere. The main pyrometamorphic phases are fassaite, gehlenite, anorthite and wollastonite. On the contrary, at 1050 °C in reducing atmosphere, gehlenite and wollastonite are diminished whereas the content of anorthite, fassaite and amorphous phase is higher. The higher vitrification is attributed to Fe²⁺ that participates either in the formation of eutectic phases or in low melting crystalline phases.     

Low temperature synthesis of anorthite based glass-ceramics via sintering and crystallization of glass-powder compacts

Anorthite based glass-ceramics were synthesized. The investigated glass compositions are located close to the anorthite-rich corner of the fluorapatite–anorthite–diopside ternary system. Glass powder compacts with mean particle size of 2 and 10 μm were prepared. Sintering behaviour, crystallization and the properties of glass-ceramics were investigated between 800 and 950 °C. In the case of specimens made from the finer particles, complete densification was achieved at a remarkably low temperature (825 °C) and the highest mechanical strength was obtained at 850 °C, but density significantly decreased at higher temperatures. The samples prepared from the larger particles exhibited higher values of density, shrinkage and bending strength within a wider temperature range (825–900 °C). Anorthite was predominantly crystallized between 850 and 950 °C, along with traces of fluorapatite. Diopside was detected only in the MgO richer compositions.     

2ZrO2·Y2O3 Thermal Barrier Coatings Resistant to Degradation by Molten CMAS: Part I,Optical Basicity Considerations and Processing

The higher operating temperatures in gas‐turbine engines enabled by thermal barrier coatings (TBCs) engender new materials issues, viz silicate particles (sand, volcanic ash, fly ash) ingested by the engine melt on the hot TBC surfaces and form calcium–magnesium–alumino–silicate (CMAS) glass deposits. The molten CMAS glass degrades TBCs, leading to their premature failure. In this context, we have used the concept of optical basicity (OB) to provide a quantitative chemical basis for the screening of CMAS‐resistant TBC compositions, which could also be extended to environmental barrier coatings (EBCs). By applying OB difference considerations to various major TBC compositions and two types of important CMASs—desert sand and fly ash—the 2ZrO₂·Y₂O₃ solid solution (ss) TBC composition, with the potential for high CMAS‐resistance, is chosen for this study. Here, we also demonstrate the feasibility of processing of 2ZrO₂·Y₂O₃(ss) air‐plasma sprayed (APS) TBC using commercially developed powders. The resulting TBCs with typical APS microstructures are found to be single‐phase cubic fluorite, having a thermal conductivity <0.9 W·(m·K)^?1 at elevated temperatures. The accompanying Part II paper presents results from experiments and analyses of high‐temperature interactions between 2ZrO₂·Y₂O₃(ss) APS TBC and the two types of CMASs.     

Thermal cycling performances of multilayered yttria-stabilized zirconia/gadolinium zirconate thermal barrier coatings

Gadolinium zirconate (Gd₂Zr₂O₇, GZO) as an advanced thermal barrier coating (TBC) material, has lower thermal conductivity, better phase stability, sintering resistance, and calcium-magnesium-alumino-silicates (CMAS) attack resistance than yttria-stabilized zirconia (YSZ, 6-8 wt%) at temperatures above 1200°C. However, the drawbacks of GZO, such as the low fracture toughness and the formation of deleterious interphases with thermally grown alumina have to be considered for the application as TBC. Using atmospheric plasma spraying (APS) and suspension plasma spraying (SPS), double-layered YSZ/GZO TBCs, and triple-layered YSZ/GZO TBCs were manufactured. In thermal cycling tests, both multilayered TBCs showed a significant longer lifetime than conventional single-layered APS YSZ TBCs. The failure mechanism of TBCs in thermal cycling test was investigated. In addition, the CMAS attack resistance of both TBCs was also investigated in a modified burner rig facility. The triple-layered TBCs had an extremely long lifetime under CMAS attack. The failure mechanism of TBCs under CMAS attack and the CMAS infiltration mechanism were investigated and discussed.     

Tailoring the EB-PVD columnar microstructure to mitigate the infiltration of CMAS in 7YSZ thermal barrier coatings

The CMAS associated degradation of 7YSZ TBC layers is one of the serious problems in the aero engines that operate in dusty environments. CMAS infiltrates into TBC at high temperatures and stiffens the TBC which ultimately loses its strain tolerance and gets delaminated. The EB-PVD technique is used to coat TBCs exhibiting a columnar microstructure on parts such as blades and on vanes. By varying the EB-PVD process parameters, columnar morphology and porosity of the 7YSZ coating is changed and its effect on the CMAS infiltration behaviour is studied in detail. Two different TBC pore geometries were created and infiltration experiments were carried out at 1250 °C and 1225 °C for different time intervals. The 7YSZ coating with more ‘feathery’ features has resulted in higher CMAS resistance by at least by a factor of 2 than its less ‘feathery’ counterpart. These results are explained on the basis of a proposed physical model.     

Calcium-magnesium-alumina-silicate (CMAS) resistant Ba2REAlO5 (RE = Yb,Er, Dy) ceramics for thermal barrier coatings

Calcium-magnesium-alumina-silicate (CMAS) attack has been a great challenge for the application of thermal barrier coatings (TBCs) in modern turbine engines. In this study, a series of prospective TBC candidate materials, Ba₂REAlO₅ (RE = Yb, Er, Dy), are found to have high resistance to CMAS attack. The rapid formation of a continuous crystalline layer on sample surface contributes to this desirable attribute. At 1250 °C, Ba₂REAlO₅ dissolve in the molten CMAS, accumulating Ba, RE and Al in the melt, which could trigger the crystallization of celsian, apatite and wollastonite crystals. Especially, the formation of the crystalline layer in the Ba₂DyAlO₅ sample is the fastest. This study also reveals that Ba is a useful element for altering CMAS composition to precipitate celsian. Thus, doping Ba²⁺ in yttria partially stabilized zirconia or other novel TBCs might be an attractive way of mitigating CMAS attack.