skip to main content


The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Thursday, May 23 until 2:00 AM ET on Friday, May 24 due to maintenance. We apologize for the inconvenience.

Title: Critical thickness of polymer‐derived ceramic coatings with particulate fillers

In this study, we demonstrate a novel environmental barrier coating processed from polymer‐derived ceramics (PDCs) with homogeneously distributed sub‐micrometer Y2O3as the filler. Under suitable conditions, dense and crack‐free coatings can be achieved for all the designed compositions with the volumetric content of Y2O3varied from 45 to 93 vol%. To process the PDC SiC–Y2O3composite coatings, Y2O3particles and SiC liquid precursor were uniformly dispersed in hexane and then dip‐coated on SiC substrates. After cross‐linking at 250°C and heat‐treated at 900°C in argon, dense and crack‐free PDC SiC–Y2O3composite coatings were formed. The effect of coating thickness and heat‐treatment temperature on the formation of cracks due to constrained pyrolysis was studied. The critical thickness for realizing crack‐free coatings of three compositions (i.e., 93, 77, and 45 vol% Y2O3) was studied for heat treatment from 1000 to 1300°C using atomic force microscope and scanning electron microscopy. As heat‐treatment temperature increases, the critical coating thickness decreases for the same coating compositions due to enhanced shrinkage at higher temperature. With higher Y2O3content, the critical thickness of the coating increased. The inert Y2O3particles reduce the amount of polymer leading to reduction in the overall constrained shrinkage of the coating during heat treatment.

more » « less
Award ID(s):
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
Date Published:
Journal Name:
International Journal of Applied Ceramic Technology
Page Range / eLocation ID:
p. 84-93
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Polymer‐derived amorphous SiCN has excellent high‐temperature stability and properties. To reduce the shrinkage during pyrolysis and to improve the high‐temperature oxidation resistance, Y2O3was added as a filler. In this study, polymer‐derived SiCN–Y2O3composites were fabricated by mixing a polymeric precursor of SiCN with Y2O3submicron powders in different ratios. The mixtures were cross‐linked and pyrolyzed in argon. SiCN–Y2O3composites were processed using field‐assisted sintering technology at 1350°C for 5 min under vacuum. Dense SiCN–Y2O3composite pellets were successfully made with relative density higher than 98% and homogeneous microstructure. Due to low temperature and short time of the heat‐treatment, the grain growth of Y2O3was substantially inhibited. The Y2O3grain size was ∼1 μm after sintering. The composites’ heat capacity, thermal diffusivity, and thermal expansion coefficients were characterized as a function of temperature. The thermal conductivity of the composites ceramics decreased as the amount of amorphous SiCN increased and the coefficient of thermal expansion (CTE) of the composites increased with Y2O3content. However, the thermal conductivity and CTE did not follow the rule of mixture. This is likely due to the partial oxidation of SiCN and the resultant impurity phases such as Y2SiO5, Y2Si2O7, and Y4.67(SiO4)3O.

    more » « less
    more » « less
  3. Abstract

    While monazite (LaPO4) does not flash sinter even at high fields of 1130 V/cm and temperatures of 1450°C, composite systems of 8YSZ–LaPO4and Al2O3–LaPO4have been found to more readily flash sinter. 8YSZ added to LaPO4greatly lowered the furnace temperature for flash to 1100°C using a field of only 250 V/cm. In these experiments,‐Al2O3alone also did not flash sinter at 1450°C even with high fields of 1130 V/cm, but composites of Al2O3–LaPO4powders flash sintered at 900‐1080 V/cm at 1450°C. Alumina–monazite (Al2O3–LaPO4) composites with compositions ranging from 25 vol% to 75 vol% Al2O3were flash sintered with current limits from 2 to 25 mA/mm2. Microstructures were evaluated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A eutectic microstructure was observed to form in all flash sintered Al2O3–LaPO4composites. With higher power (higher current limits), eutectic structures with regular lamellar regions were found to coexist in the channeled region (where both the current and the temperature were the highest) with large hexagonal‐shaped‐Al2O3grains (up to 75 m) and large irregular LaPO4grains. With lower power (lower current limits), an irregular eutectic microstructure was dominant, and there was minimal abnormal grain growth. These results indicate that Al2O3–LaPO4is a eutectic‐forming system and the eutectic temperature was reached locally during flash sintering in regions. These eutectic microstructures with lamellar dimensions on the scale of 100 nm offer potential for improved mechanical properties.

    more » « less
  4. Ever-increasing demands for energy, particularly being environmentally friendly have promoted the transition from fossil fuels to renewable energy.1Lithium-ion batteries (LIBs), arguably the most well-studied energy storage system, have dominated the energy market since their advent in the 1990s.2However, challenging issues regarding safety, supply of lithium, and high price of lithium resources limit the further advancement of LIBs for large-scale energy storage applications.3Therefore, attention is being concentrated on an alternative electrochemical energy storage device that features high safety, low cost, and long cycle life. Rechargeable aqueous zinc-ion batteries (ZIBs) is considered one of the most promising alternative energy storage systems due to the high theoretical energy and power densities where the multiple electrons (Zn2+) . In addition, aqueous ZIBs are safer due to non-flammable electrolyte (e.g., typically aqueous solution) and can be manufactured since they can be assembled in ambient air conditions.4As an essential component in aqueous Zn-based batteries, the Zn metal anode generally suffers from the growth of dendrites, which would affect battery performance in several ways. Second, the led by the loose structure of Zn dendrite may reduce the coulombic efficiency and shorten the battery lifespan.5

    Several approaches were suggested to improve the electrochemical stability of ZIBs, such as implementing an interfacial buffer layer that separates the active Zn from the bulk electrolyte.6However, the and thick thickness of the conventional Zn metal foils remain a critical challenge in this field, which may diminish the energy density of the battery drastically. According to a theretical calculation, the thickness of a Zn metal anode with an areal capacity of 1 mAh cm-2is about 1.7 μm. However, existing extrusion-based fabrication technologies are not capable of downscaling the thickness Zn metal foils below 20 μm.

    Herein, we demonstrate a thickness controllable coating approach to fabricate an ultrathin Zn metal anode as well as a thin dielectric oxide separator. First, a 1.7 μm Zn layer was uniformly thermally evaporated onto a Cu foil. Then, Al2O3, the separator was deposited through sputtering on the Zn layer to a thickness of 10 nm. The inert and high hardness Al2O3layer is expected to lower the polarization and restrain the growth of Zn dendrites. Atomic force microscopy was employed to evaluate the roughness of the surface of the deposited Zn and Al2O3/Zn anode structures. Long-term cycling stability was gauged under the symmetrical cells at 0.5 mA cm-2for 1 mAh cm-2. Then the fabricated Zn anode was paired with MnO2as a full cell for further electrochemical performance testing. To investigate the evolution of the interface between the Zn anode and the electrolyte, a home-developed in-situ optical observation battery cage was employed to record and compare the process of Zn deposition on the anodes of the Al2O3/Zn (demonstrated in this study) and the procured thick Zn anode. The surface morphology of the two Zn anodes after circulation was characterized and compared through scanning electron microscopy. The tunable ultrathin Zn metal anode with enhanced anode stability provides a pathway for future high-energy-density Zn-ion batteries.

    Obama, B., The irreversible momentum of clean energy.Science2017,355(6321), 126-129.

    Goodenough, J. B.; Park, K. S., The Li-ion rechargeable battery: a perspective.J Am Chem Soc2013,135(4), 1167-76.

    Li, C.; Xie, X.; Liang, S.; Zhou, J., Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc‐ion Batteries.Energy & Environmental Materials2020,3(2), 146-159.

    Jia, H.; Wang, Z.; Tawiah, B.; Wang, Y.; Chan, C.-Y.; Fei, B.; Pan, F., Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.Nano Energy2020,70.

    Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T., Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives.Nanomicro Lett2022,14(1), 42.

    Yang, Q.; Li, Q.; Liu, Z.; Wang, D.; Guo, Y.; Li, X.; Tang, Y.; Li, H.; Dong, B.; Zhi, C., Dendrites in Zn-Based Batteries.Adv Mater2020,32(48), e2001854.


    This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

    Figure 1


    more » « less
  5. Tantalum carbide (TaC) and hafnium carbide (HfC) have some of the highest melting temperatures among the transition metal carbides, borides, and nitrides, making them promising materials for high‐speed flight and high‐temperature structural applications. Solid solutions of TaC and HfC are of particular interest due to their enhanced oxidation resistance compared to pure TaC or HfC. This study looks at the effect of Hf content on the oxidation resistance of TaC–HfC sintered specimens. Five compositions are fabricated into bulk samples using spark plasma sintering (2173 K, 50 MPa, 10 min hold). Oxidation behavior of a subset of the compositions (100 vol% TaC, 80 vol% TaC + 20 vol% HfC, and 50 vol% TaC + 50 vol% HfC) is analyzed using an oxyacetylene torch for 60 s. The TaC–HfC samples exhibit a reduction in the oxide scale thickness and the mass ablation rate with increasing HfC content. The improved oxidation resistance can be attributed to the formation of a Hf6Ta2O17phase. This phase enhances oxidation resistance by reducing oxygen diffusion and serving as a protective layer for the unoxidized material. The superior oxidation resistance of TaC–HfC samples makes these materials strong contenders for the development of high‐speed flight coatings.

    more » « less