Calcium-magnesium-alumino-silicate induced degradation of La2(Zr0.7Ce0.3)2O7/YSZ double-ceramic–layer thermal barrier coatings prepared by electron beam-physical vapor deposition

During last decades, much effort has been made to develop new alternative thermal barrier coating (TBC) to traditional YSZ for applications above 1250oC. La2(Zr0.7Ce0.3)2O7(LZ7C3) is deemed as a very promising TBC candidate for advanced gas turbine because of its extremely low thermal conductivity, high sintering resistance and phase stability from room temperature to 1600oC. Thermal cycling with a gas burner showed that the LZ7C3/YSZ double-ceramic-layer (DCL) coatings prepared by electron beam-physical vapor deposition (EB-PVD) or atmospheric plasma spraying had a much longer lifetime than that of YSZ coating at 1250± 50oC.The use of the new TBC can allow higher gas temperatures, resulting in further improved thermal efficiency and engine performance. However, at these high operating temperatures, TBCs become susceptible to attack by calcium-magnesium-alumino-silicate (CMAS, relative to the main chemical components Ca, Mg, Al and Si) deposits resulting from the ingestion of siliceous minerals (dust, sand, volcanic ash, runway debris) with the intake air. CMAS becomes molten at temperatures above 1200oC and then rapidly penetrates the TBCs by capillary force, resulting in the loss of strain tolerance and premature failure of the coatings. In this paper, CMAS induced degradation of LZ7C3/YSZ DCL coatings prepared by EB-PVD method were investigated. Hot corrosion tests were performed at 1250oC at durations varying from 0.5 h to 24 h. It is observed that the infiltration of CMAS in the intercolumnar gaps was largely suppressed in the case of EB-PVD LZ7C3 coating. The penetration depth rarely exceeded 40 μm below the original surface even after 24 h exposure at 1250oC. This was ascribed to rapid dissolution of the LZ7C3 and essentially concurrent formation of a sealing layer made of crystalline apatite and fluorite phases, which is consistent with the observation on Gd2Zr2O7. However, large vertical cracks would form in the EB-PVD LZ7C3 coating during thermal cycling as a result of re-crystallization, sintering and thermal expansion mismatch between ceramic coating and substrate. These vertical cracks can also act as channels to CMAS melt infiltration. Since the kinetics of the dissolve-reprecipitation reaction was slower than the infiltration rate of CMAS in the vertical crack, the majority of vertical cracks were not sealed. As a result, CMAS flowed down to the LZ7C3/YSZ interface along the vertical cracks, and then easily penetrated the YSZ buffer layer by capillary force. Chemical interaction also occurred in the YSZ buffer layer. What\u27s more, the YSZ layer in the DCL coating even underwent a severer CMAS attack than the single YSZ coating. After 4 h CMAS exposure, the YSZ layer of the LZ7C3/YSZ bilayer coating was totally dissolved by molten CMAS followed by precipitation of a large number of globular ZrO2 particles, while the single YSZ coating just suffered a slight degradation in the same experimental conditions and still kept its columnar structure. The probable reason was that the CMAS melt in the YSZ layer of the DCL coating had a higher CaO/SiO2 ration than the original CMAS composition due to the formation of apatite phase when CMAS reacted with the upper LZ7C3 layer. The initial Si: Ca ratio (Si: Ca≈1.4) in CMAS melt is less than the corresponding apatite (Si: Ca≈3), leading to progressive CaO enrichment during apatite crystallization. For this reason, it is suggested that the effectiveness of the CMAS mitigation strategy for YSZ TBCs by adopting a so-called CMAS-resistant top layer needs to be assessed in the context of more realistic conditions. If the formation of large vertical cracks in TBCs was not avoided, this CMAS mitigation approach may not as effective as expected

Design and synthesis of a new mannitol stearate ester-based aluminum alkoxide as a novel tri-functional additive for poly(vinyl chloride) and its synergistic effect with zinc stearate

Thermal stabilizers, lubricant, and plasticizers are three crucial additives for processing poly(vinyl chloride) (PVC). In this study, a new mannitol stearate ester-based aluminum alkoxide (MSE-Al) was designed and synthesized as a novel additive for PVC. The thermal stability and processing performance of PVC stabilized by MSE-Al were evaluated by the Congo red test, conductivity measurement, thermal aging test, ultravioletevisible (UV–Vis) spectroscopy test, and torque rheometer test. Results showed that the addition of MSE-Al could not only markedly improve the long-term thermal stability of PVC, but also greatly accelerate the plasticizing and decrease the balance torque, which demonstrated that MSE-Al possessed a lubricating property. Thus, MSE-Al was demonstrated to be able to provide tri-functional additive roles, e.g., thermal stabilizer, plasticizer, and lubricant. The test results for the thermal stability of PVC indicated that the initial whiteness of PVC stabilized by MSE-Al was not good enough, thus the synergistic effect of MSE-Al with zinc stearates (ZnSt2) on the thermal stability of PVC was also investigated. The results showed that there is an appreciable synergistic effect between MSE-Al and ZnSt2. The thermal stabilization mechanism and synergism effect of MSE-Al with ZnSt2 are then discussed

Metal-free graphene-carbon nitride hybrids for photodegradation of organic pollutants in water

Hybrid photocatalysts of graphitic carbon nitride (g-C3N4) and reduced graphene oxide (rGO) composites were prepared in one-pot via a thermal condensation of melamine with different amounts of graphene oxide (GO). As metal-free hybrids, the prepared photocatalysts presented enhanced performances in photooxidation of both methylene blue and phenol in water solutions under various light irradiations. The level of rGO significantly affected MB photodegradation efficiencies. The introduced graphene can improve the MB adsorption and optical absorption in visible light region, therefore enables the hybrids to efficiently degrade MB under visible light with wavelengths longer than 430 nm. The metal-free photocatalysts were also able to degrade phenol effectively and the effects of catalyst loading and initial phenol concentration were investigated. This study provided an efficient and environmentally benign photocatalyst for degradation of organic pollutants in water, with complete prevention of secondary contamination from metal-leaching

Spatiotemporal Variation of Driving Forces for Settlement Expansion in Different Types of Counties

Understanding the process of settlement expansion and the spatiotemporal variation of driving forces is the foundation of rational and specific planning for sustainable development. However, little attention has been paid to the spatiotemporal differences of driving forces among different counties, especially when they are representatives of different development types. This study used Guanyun, Kunshan and Changshu as case studies, and binary logistic regression was employed. The results showed that the expansion rates of Kunshan and Changshu were 5.55 and 3.93 times higher than that of Guanyun. The combinations and relative importance of drivers varied with counties and periods. The change in the number of driving forces can be divided into three stages: increasing stage, decreasing stage, and stable stage. In the relatively developed counties, Kunshan and Changshu, the importance of population is decreased, while it remain an important factor in the less developed county, Guanyun. In addition, the effect of GDP stays the same in Kunshan while it becomes the most important factor in Changshu. The distance to the main road and the distance to town are increasingly important in Kunshan and Guanyun, and distance to town has been the only common factor in the last period, indicating the discrepancy is increased. The relative importance of distance to a lake in Kunshan and Changshu increased, reflecting the role of increasing tourism in accelerating settlement expansion

Interface engineering of electronic properties of graphene/boron nitride lateral heterostructures

Heterostructures are often expected to be of enhanced electronic properties compared with homogeneous ones. Valuable experimental efforts have been devoted to the fabrication of graphene/hexagonal boron nitride (hBN) lateral heterostructures. It has been shown that abrupt interface between graphene and hBN could form in a controllable manner at the atomic scale. We thus investigate the electronic properties of such new hybrid structures by systematically considering possible interface configurations. Our results obtained with density-functional theorem reveal that interface has significant impact on electronic properties. Specifically, for heterostructures with a zigzag type of interface, electronic states are found to be spin-polarized, and a half-metallic phase is identified when the graphene domain is terminated with zigzag edges. For heterostructures with an armchair type of interface, electronic states display a robust semiconducting behavior. The novelty and diversity in electronic properties have implications for the design of new atomic devices in two dimensions based on lateral heterostructures.National Basic Research Program of China [2012CB932703, 2012CB932700]; National Natural Science Foundation of China [91221202, 11504366, 91421303, 61321001]SCI(E)[email protected]; [email protected]