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1.
Thermochemical interactions between Ca2Y8(SiO4)6O2 apatite, a potential environmental barrier coating (EBC) material, and a synthetic CMAS having the composition 23.3 CaO - 6.4 MgO - 3.1 Al2O3 - 62.5 SiO2 - 4.1 Na2O - 0.5 K2O - 0.04 Fe2O3 mole % were investigated. Pellets of apatite + CMAS powder and hot-pressed apatite disc-CMAS couples were annealed at 1200–1500 °C for 1–50 hours in air. Powder X-ray diffraction (XRD) was used to identify the phases present. Polished cross-sections of the heat treated pellets and diffusion couples were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), high angle annular dark field (HAADF) imaging, selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDS). Ca3Y2(Si3O9)2 cyclosilicate, apatite, and amorphous phases were present in the samples heat treated at 1200 and 1300 °C, whereas no cyclosilicate was detected in samples annealed at 1400 and 1500 °C. A distinct cyclosilicate layer was observed at the apatite-CMAS interface in the diffusion couples heat treated at 1200 and 1300 °C. However, at 1400 and 1500 °C, due to its much lower viscosity, CMAS quickly infiltrated the apatite substrate through pores and along the grain boundaries and no cyclosilicate was observed; the apatite grains dissolved in molten CMAS followed by re-precipitation of apatite needles within an amorphous phase on cooling.  相似文献   

2.
Calcium-magnesium-alumino-silicates (CMAS) melt attack has been a critical issue for the thermal barrier coatings (TBCs) with ever-increasing engine operating temperature. In this study, a novel CMAS-resistant material apatite-type Gd10(SiO4)6O3 is developed for TBCs application based on thermodynamic equilibrium design. The chemical reaction of Gd10(SiO4)6O3 bulk and CMAS melt is investigated at 1300°C. The CMAS corrosion resistance of Gd10(SiO4)6O3 bulk is evaluated and compared with the well-studied CMAS-resistant material Gd2Zr2O7 (GZO). It is found that Gd10(SiO4)6O3 shows a significantly enhanced CMAS resistance, including lower intrinsic CMAS infiltration rate (~1.09 μm/h1/2) and smaller infiltration upper limit (50-62 μm) for a 20 mg/cm2 CMAS deposition. More importantly, for Gd10(SiO4)6O3, the CMAS infiltration only alters the composition but does not change the crystal structure or destroy microstructural integrity. The reaction mechanism is elucidated as following two stages: (a) surface Gd10(SiO4)6O3 quickly transforms into Ca2Gd8(SiO4)6O2 in suit by interdiffusion with CMAS melt and then is thermodynamically stable with CMAS melt, thereby effectively inhibiting the further CMAS infiltration and (b) with the ongoing interdiffusion of Gd/Ca, the CMAS-infiltrated layer slowly thickens and follows a parabolic law. Meanwhile, the CMAS melt gradually precipitates Ca2Gd8(SiO4)6O2 and CaAl2Si2O8 (anorthite) until the melt is exhausted.  相似文献   

3.
Environmental barrier coatings (EBCs) prevent the oxidation of ceramic matrix composites (CMC), which are used as components in gas turbines. However, EBCs deteriorate more rapidly in real environments, molten silicate deposits accelerate the deterioration of EBCs. In this study, high-temperature behavior sintered Gd2Si2O7 with calcia-magnesia-alumina-silica (CMAS) melt at 1400 °C for 0.5, 2, 12, 48, and 100 h was investigated. HT-XRD results showed that at 1300 °C, CMAS and Gd2Si2O7 chemically reacted to form Ca2Gd8(SiO4)6O2 (apatite). The reaction layer became thicker as the heat-treatment time increased, and the thickness of the reaction layer has increased following a parabolic curve. With the extension of the reaction time from 0.5 to 100 h, the thickness of the reaction layer increased from approximately 98 to 315 µm. It was confirmed that Ca2Gd8(SiO4)6O2 grew vertically on the Gd2Si2O7 surface. Vertical and horizontal cracks were found after reacting at 1400 °C for 100 h, but no interfacial delamination occurred in this study. In addition, the effects of CaO:SiO2 molar ratios, monosilicates (RE2SiO5) and disilicates (RE2Si2O7), heat-treatment time, and cation size were determined and compared with the results of previous studies (Gd2SiO5, Yb2SiO5, and Er2Si2O7).  相似文献   

4.
The Gd2SiO5 performed high-temperature corrosion behavior on calcium–magnesium– aluminosilicate (CMAS) for environmental barrier coatings (EBCs). The synthesized Gd2O3-SiO2 powder was prepared to fabricate a sintered Gd2SiO5 by spark plasma sintering (SPS) at 1400°C for 20 min. CMAS was sprinkled on the sintered Gd2SiO5 surface and exposed for 2, 12, and 48 h at 1400°C by isothermal heat treatment. The main corrosion factor is Ca, and Ca2Gd8(SiO4)6O2 phase is formed by reacting with Gd2SiO5. Extended morphology of Ca2Gd8(SiO4)6O2 particles observed in the reaction area become thicker as the heat treatment time increases as the CMAS is dissolved. According to the results of high-temperature X-ray diffraction (HT-XRD) and differential scanning calorimetry (DSC), CMAS melted at 1243°C or a higher temperature formed the reaction area. The Ca2Gd8(SiO4)6O2 phase was recrystallized and grown due to the reaction of Gd2SiO5 and Ca of the CMAS components.  相似文献   

5.
Improvement of the calcium-magnesium aluminosilicate (CMAS) infiltration mitigation concept in thermal barrier coatings (TBC) requires fundamental data on thermochemical reaction involving rare-earth oxide candidate as ZrO2 alloying element. This study investigates, through a model approach, Gd2O3 dissolution at 1200 °C in a synthetic model CAS melt (64.4SiO2–9.3Al2O3–26.4CaO mol. %) and the stability of the precipitated Gd-apatite Ca2Gd8(SiO4)6O2 and Ca3Gd2(Si3O9)2 cyclosilicate phases. The two Gd-rich silicates have been synthesized by solid-state reaction and then characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The interactions of Gd2O3, Gd-apatite and Gd-cyclosilicate with CAS have been observed by scanning electron microscope (SEM) after various times of contact at 1200 ̊C, giving information about dissolution/precipitation processes. Dissolution kinetics has been evaluated by electron probe microanalysis (EPMA) measurements in the CAS melt. A discussion is finally provided concerning the thermodynamic stability of all phases of the system and confronted with kinetics considerations.  相似文献   

6.
A calcium-magnesium aluminosilicate (CMAS) glass was prepared by melting a sample of desert sand to evaluate the high-temperature interactions between molten CMAS and yttrium disilicate (Y2Si2O7), an environmental barrier coating (EBC) candidate material. Cold-pressed pellets of 80?wt% Y2Si2O7 powder and 20?wt% CMAS glass powder were heat treated at 1200?°C, 1300?°C, 1400?°C and 1500?°C for 20?h in air. The resulting phases were evaluated using powder X-ray diffraction. In the second set of experiments, free standing hot-pressed Y2Si2O7 substrates with cylindrical wells were filled with CMAS powder to a loading of ~35?mg/cm2 and heat treated in air at 1200?°C, 1300?°C, 1400?°C and 1500?°C for 20?h. Scanning electron microscopy, energy-dispersive spectroscopy and electron microprobe analysis were used to evaluate the microstructure and phase compositions of specimens after heat treatment. An oxyapatite silicate (Ca2Y8(SiO4)6O2) phase was identified in all specimens after CMAS exposure regardless of heat treatment temperature. Apatite appeared to form by dissolution of Y2Si2O7 into molten CMAS, reacting with CaO in the melt according to the reaction 4Y2Si2O7 +?2CaO → Ca2Y8(SiO4)6O2 +?2SiO2, and followed by precipitation of the apatite phase.  相似文献   

7.
The thermochemical behavior of EBC candidate materials yttrium disilicate (Y2Si2O7) and ytterbium disilicate (Yb2Si2O7) was evaluated with three calcium-magnesium-aluminosilicate (CMAS) glasses possessing CaO:SiO2 ratios relevant to gas turbine systems. Pellet mixtures of 50 mol% EBC powder to 50 mol% CMAS glass powder were heat treated at 1200°C, 1300°C, and 1400°C. The products of these interactions were evaluated using X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. Above glass melting temperatures, exposure of the disilicates primarily resulted in dissolution into the molten glass followed by precipitation of a Ca2RE8(SiO4)6O2 (RE = Yb3+, Y3+) apatite-type silicate and/or rare earth disilicate. In glasses with high CaO concentrations, apatite readily forms while the disilicate material is consumed by the reaction. As CaO content decreases, the disilicate phase becomes the main reaction product. Overall, reactions with yttrium disilicate favored more apatite crystallization than ytterbium disilicate. The viability of using these disilicates in various operating environments is discussed.  相似文献   

8.
《Ceramics International》2022,48(12):16499-16504
The thermochemical degradation of hafnium silicate (HfSiO4) was investigated with a molten calcium-magnesium-aluminosilicate (CMAS) glass relevant to gas turbine engine applications. Sintered HfSiO4 coupons were fabricated, within which wells were drilled and filled with CMAS glass powder at a loading of ~35 mg/cm2. Samples were heat treated at 1200°C, 1300°C, 1400°C, and 1500°C for 1 h, 10 h, and 50 h. At 1200°C and 1300°C, slow formation of a Ca2HfSi4O12 cyclosilicate phase was observed at the HfSiO4-CMAS interface. At 1300°C and higher, rapid infiltration of CMAS into the material along the grain boundaries was observed. Initial conjecture into CMAS degradation mechanisms of HfSiO4 are presented herein.  相似文献   

9.
Rare-earth (RE) zirconates, such as gadolinium zirconate (GZ), gained much attraction to be used for the next generation TBC. A double-layer and triple-layer TBC were deposited using the suspension and solution precursor high velocity oxy fuel (HVOF) thermal spray. A dense solution precursor GZ layer was intended to minimise the crack propagation from underneath, thereby inhibiting the CMAS infiltration. In the furnace cycling test, the double- and triple-layer coatings had a comparable cyclic lifetime. For the CMAS test, both the double- and triple-layer coatings were exposed to CMAS at 1250 °C for 30 mins. The CMAS deposits melted and infiltrated both coatings through the dense vertical cracks (DVCs). Interestingly, the GZ reacted with the molten CMAS to form a gadolinium apatite phase (Ca2Gd8(SiO4)6O2) that was detected in the double- and triple-layer TBC. Both the double- and triple-layer TBCs succeeded in reacting with CMAS.  相似文献   

10.
In this work we reported a new class of rare earth oxy-apatite, RE9.33(SiO4)6O2, with superior molten silicate resistant capability which shows promising application for thermal barrier coatings (TBCs). Three RE elements with different ion radius, i.e., Gd, Nd and La, were selected to prepare RE9.33(SiO4)6O2 bulk using co-precipitation and pressless-sintering. After 8-h CMAS attack at 1300 °C, the specimens exhibited a dense, continuous reprecipitated layer at RE-apatite/CMAS interface, which is predominantly controlled by a dissolution-reprecipitation mechanism distinguishing from the sacrificial material which is usually with reaction layer being formed. With an increase of ion radius, apatite is easier to crystallize in the melt.  相似文献   

11.
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.  相似文献   

12.
Calcium-magnesium-alumina-silicate (CMAS) attack has been considered as a significant failure mechanism for thermal barrier coatings (TBCs). As a promising series of TBC candidates, rare-earth phosphates have attracted increasing attention. This work evaluated the resistance characteristics of LnPO4 (Ln = Nd, Sm, Gd) compounds to CMAS attack at 1250 °C. Due to the chemical reaction between molten CMAS and LnPO4, a dense, crack-free reaction layer, mainly composed of Ca3Ln7(PO4)(SiO4)5O2 apatite, CaAl2Si2O8 and MgAl2O4, was formed on the surface of compounds, which had positive effect on suppressing CMAS infiltration. The depth of CMAS penetration in LnPO4 (Ln = Nd, Sm, Gd) decreased in the sequence of NdPO4, SmPO4 and GdPO4. GdPO4 had the best resistance characteristics to CMAS attack among the three compounds. The related mechanism was discussed based on the formation ability of apatite phase caused by the reaction between molten CMAS and LnPO4.  相似文献   

13.
《Ceramics International》2022,48(12):17369-17375
The suitability of sintered erbium disilicate (Er2Si2O7) as an environmental barrier coatings (EBCs) for gas turbine applications was assessed by characterizing its high-temperature corrosion behavior in contact with a synthetic calcia-magnesia-alumina-silica (CMAS) melt. Er2Si2O7 was fabricated using spark plasma sintering at 1400 °C for 20 min. Corrosion tests were performed by coating sintered Er2Si2O7 pellets with CMAS and heating them to 1400 °C for 2, 12, and 48 h. High-temperature X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analysis were used to identify and analyze the reaction products. The two materials were found to react chemically to form an apatite phase, Ca2Er8(SiO4)6O2, at their interface. The Ca2Er8(SiO4)6O2 grains were observed to have shard-like morphologies oriented perpendicular to the Er2Si2O7 surface; the reaction layer thickened with increasing heat-treatment time, with the thickness after exposure for 48 h approximately three times the thickness after 2 h.  相似文献   

14.
Environmental barrier coatings (EBCs) applied to gas-turbine components require excellent corrosion resistance to molten siliceous debris such as sand or volcanic ash in high-temperature environments while maintaining mechanical integrity. To date, most research has focused on single-phase rare-earth (RE) disilicates as candidate EBC materials, but here we report the superior corrosion resistance of a dual-phase disilicate composite, namely Gd2Si2O7/Sc2Si2O7 (70/30 vol%). EBSD measurements of cross-sections of the EBC after exposure to a calcium magnesium alumino-silicate (CMAS) for 0.5, 2, 12, and 48 h at 1400 °C reveal that, unlike in single-phase systems, the CMAS reaction layer consists of two distinct sublayers. The inner sublayer consists of a mixture of Ca2Gd8(SiO4)6O2 and Sc2Si2O7 crystals in a Ca-depleted glassy matrix, whereas the thinner outer region contains larger, elongated Ca2Gd8(SiO4)6O2 crystals oriented perpendicular to the composite surface and devoid of any Sc2Si2O7 crystals. The total thickness of the reaction layer is found to be about 20% less compared to that of single-phase Gd2Si2O7 under the same conditions, indicating that dual-phase RE-disilicate composites are a promising materials system for increasing the lifetime performance of EBCs.  相似文献   

15.
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.  相似文献   

16.
《Ceramics International》2022,48(6):8286-8296
Molten calcium magnesium alumina-silicates (CMAS) represent a challenge for the current generation of rare earth silicates environmental barrier coatings (EBCs). Their interaction with ytterbium disilicate (Yb2Si2O7) free-standing coatings deposited using thermal spraying technique has been studied to further understand the reaction mechanisms. Three coatings, deposited with different porosity levels and thickness, representing traditional EBCs (<3% porosity and ~350 μm thickness) and abradable coatings (~20% porosity and 500–1000 μm thickness) were exposed to CMAS at 1350 °C. The results show that higher porosity levels facilitates CMAS infiltration in the first hour of exposure, in combination with infiltration through the inter-splat boundaries. Preferential dissolution of ytterbium monosilicate (Yb2SiO5) takes place, forming a 10–15 μm Ca2Yb8(SiO4)6O2 apatite layer as the reaction product, producing a network of fine porosity (<10 μm) as the inter-splat boundary material is consumed. After exposure for 48 h, CMAS has completely infiltrated all three coatings, with apatite crystals present across the coatings, up to a depth of ~550 μm. Despite the extensive CMAS infiltration and apatite formation, no damage could be observed in any of the coatings, providing a promising first step for environmental barrier abradable coatings.  相似文献   

17.
Hot corrosion behavior was evaluated by gadolinium monosilicate (Gd2SiO5) with volcanic ash for environmental barrier coatings (EBCs). Sintered Gd2SiO5 was prepared by the spark plasma sintering (SPS) method at 1400 °C for 20 min, and high-temperature corrosion resistance against of volcanic ash was evaluated at 1400 °C for 2 h, 12 h, and 48 h. The surface region of sintered Gd2SiO5 was partially dissolved in molten volcanic ash, creating a chemically reacted area. The formation of the elongated morphology of Ca2Gd8(SiO4)6O2 grains observed in the reaction area is thicker with increasing heat-treatment time as the volcanic ash dissolves. In addition, high-temperature X-ray diffraction was carried out to identify the dynamics of phase evaluation in the volcanic ash and Gd2SiO5. According to the results, corrosion occurs due to reaction of the Gd2SiO5 phase and the Ca component of volcanic ash at 1300 °C, and the Ca2Gd8(SiO4)6O2 phase is generated.  相似文献   

18.
《Ceramics International》2023,49(16):26578-26588
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.  相似文献   

19.
With the increased demand for high operating temperature of gas turbine engines, corrosion by molten calcium-magnesium-alumino-silicate (CMAS) exhibits a significant challenge to the development of durable environmental barrier coatings (EBCs). EBC candidates, γ-Y2Si2O7, β-Yb2Si2O7, and β-Lu2Si2O7 were explored on their corrosion resistance to CMAS melts at 1300 °C and 1500 °C for 50 h. Interaction and degradation mechanisms were investigated and the corrosion behaviors showed different trends at high temperatures. At 1300 °C, RE2Si2O7 dissolves into CMAS melts and apatite phases reprecipitate forming a thick recession layer. However, when the temperature increases to 1500 °C, CMAS melts vigorously penetrate through the grain boundary of RE2Si2O7 and ‘blister’ cracks form throughout the samples. The reduced grain boundary stability at 1500 °C promotes the penetration of CMAS melts in RE2Si2O7. Grain boundary engineering is critically demanded to optimize CMAS corrosion at high temperatures.  相似文献   

20.
《Ceramics International》2021,47(22):31625-31637
Experimental investigations of Yb2Si2O7 pellet exposed to Calcium-Ferrum-Alumina-Silicate (CFAS) at 1400 °C in ambient air were carried out to reveal corrosion reaction between molten silicate deposit and Yb2Si2O7. Phase transformation, microstructure evolution and reaction mechanism were evaluated. Results indicated that the corrosion process was accompanied by the infiltration of CFAS melt, the dissolution of Yb2Si2O7 and the reprecipitation of Yb2Si2O7 and Ca2Yb8(SiO4)6O2 apatite as reaction product. The formation of apatite decreased the concentration of Ca2+ in the melt. After CFAS exposure at 1400 °C for 30 h, the thickness of the apatite layer stopped increasing due to insufficient Ca2+ content, and remained at about 115.4 μm. However, the infiltration depth of CFAS melt increased with the extending corrosion duration and increasing deposit content. And the infiltration rate was preliminarily found to first decrease and then increase with time. Most of the residual CFAS were crystallized into garnet (Ca3Fe2(SiO4)3 and Yb3Fe5O12) and mayerite (Ca12Al14O33), while a small volume of amorphous glass was dispersed among the garnet and mayerite grains.  相似文献   

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