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At least 1,261 records · Page 70

In situ characterization of foreign object damage (FOD) in environmental-barrier-coated silicon carbide (SiC) ceramic

Environmental barrier coatings (EBCs) protect advanced ceramics and ceramic matrix composites (CMCs) from oxidation and corrosion in gas turbine engine environments. Foreign object damage (FOD), where debris impact the protective coatings, is a critical hazard which limits the turbine durability. Despite previous efforts to understand FOD in EBCs, a detailed understanding of the fundamental transient damage mechanisms is still lacking. In the current work, the real-time FOD behavior of a Mullite / Silicon EBC was visualized via a dynamic synchrotron X-ray source in phase contrast imaging (PCI) configuration. Prior to the in situ FOD experiments, the microstructure and composition of the coating were respectively characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD). The variation in the properties of the debris was modeled by ~ 1.5 mm diameter Partially Stabilized Zirconia (PSZ) and Silicon Nitride (Si 3 N 4 ) spheres. A modified light-gas gun setup, synchronized with the X-ray beam, was used to propel the projectiles at velocities ranging between 300 and 355 m·s -1 . Coated samples were impacted under a fully backed support configuration and at normal incidence. Coating penetration and delamination, as well as projectile deformation at the bond coat resulted for FOD by PSZ spheres. Comparatively, projectile fracture, with subsequent rebound of fragments, as well as complete coating penetration and delamination at the substrate interface occurred for FOD by Si 3 N 4 spheres. It should be noted that only cone cracking was observed for FOD by PSZ spheres while back surface cracking was present for both projectile types. Qualitative understanding of the driving forces for the observed damage mechanisms were provided.

36 MATERIALS SCIENCE↗

A far‐red‐emitting (Gd,Y) 3 (Ga,Al) 5 O 12 :Mn 2+ ceramic phosphor with enhanced thermal stability for plant cultivation

Abstract As for plants, far‐red (FR) light with wavelength from 700 nm to 740 nm is critical for processes of photosynthesis and photomorphogenesis. Light‐controlled development depends on light to control cell differentiation, structural and functional changes, and finally converge into the formation of tissues and organs. Phosphor converted FR emission under LED excitation is a cost‐effective and high‐efficient way to provide artificial FR light source. With the aim to develop an efficient FR phosphor that can promote the plant growth, a series of gadolinium yttrium gallium garnet (GYGAG) transparent ceramic phosphors co‐doped with Mn 2+ and Si 4+ have been fabricated via chemical co‐precipitation method, followed sintered in O 2 and hot isostatic pressing in this work. Under UV excitation, the phosphor exhibited two bright and broadband red emission spectra due to Mn 2+ : 4 T 1 → 6 A 1 spin‐forbidden transition, and one of which located in the right FR region. And then, Ce 3+ ions were co‐doped as the activator to enhance the absorption at blue light region and the emission of Mn 2+ . It turns out that the emission band of GYGAG transparent ceramic phosphors matches well with the absorption band of phytochrome P FR , which means they are promising to be applied in plant cultivation light‐emitting diodes (LEDs) for modulating plant growth. Besides, the thermal stability of this material was investigated systematically, and an energy transferring model involves defects was also proposed to explain the phenomenon of abnormal temperature quenching.

Qiu, Xuting↗

High-entropy boride–carbide ceramics by sequential boro/carbothermal synthesis

We report a dual-phase high-entropy boride/carbide ceramic with fine grain size was synthesized by a sequential boro/carbothermal process. In the first step, a Hf-Nb-Ta-Ti-Zr-containing carbide was synthesized by carbothermal reduction of oxides followed by reaction of the carbide with B4C and ZrH2 to convert part of the carbide to boride. The resulting composition was ~29 vol% high-entropy boride with an average grain size of ~1.1 µm. Solid solution formation occurred at the densification temperature of 1900°C resulting in a relative density higher than 99%. The Vickers’ hardness was 26.5 ± 1.4 GPa. This is the first report of synthesizing dual-phase boride-carbide high-entropy ceramics from carbothermally synthesized, high-entropy carbide powders.

36 MATERIALS SCIENCE↗

Size effects in 3D–printed polymer–derived, zirconium diboride–reinforced ceramic composites

Preceramic polymers are of interest for use in many manufacturing techniques such as injection molding, ceramic fiber infiltration, and additive manufacturing. However, off-gassing of low molecular weight oligomers occurs when these polymers cure, potentially leading to porosity in the cured part. Here to study how porosity and strength are affected by the size of the printed part, and the presence of a high surface area nano-scale filler, polycarbosilane (PCS) microrods of varying diameter were fabricated via direct ink writing (DIW), an additive manufacturing technique, with two ink formulations containing either zirconium diboride (ZrB 2 ) alone, or ZrB 2 and fumed alumina (FA). Sets of microrods were printed in a range of sizes by using print nozzles of 450, 634, 979, 1 346, or 1 702 μm in diameter, which were thermally cured, pyrolyzed to form ceramic composite microrods, and tested in 3-pt flexure. Porosity increased with increasing diameter, while failure strength decreased. For a given nozzle size, the microrods containing FA displayed lower porosity and higher strength (up to ~500 MPa) compared to the microrods containing only ZrB 2 . Weibull strength analysis was performed on each group of microrods and shows that the addition of FA increased Weibull modulus from 4.63 ± 1.56 to 9.35 ± 0.601. In conjunction with optical microscopy, this analysis indicates two distinct flaw populations in the printed materials, porosity which arises during the curing step and cracking which arises during pyrolysis of the larger specimens.

36 MATERIALS SCIENCE↗

Redesigning protonic ceramic electrochemical cells to lower the operating temperature

Protonic ceramic electrochemical cells (PCECs) can operate at intermediate temperatures (450° to 600°C) for power generation and hydrogen production. However, the operating temperature is still too high to revolutionize ceramic electrochemical cell technology. Lowering the operating temperature to <450°C will enable a wider material choice and reduce system costs. We present approaches to redesigning PCECs via readily fabricated single-grain–thick, chemically homogeneous, and robust electrolytes and a nano-micro positive electrode. At 450°C, the PCECs achieve a peak power density of 1.6 watt per square centimeter on H 2 fuel, 0.5 watt per square centimeter on NH 3 fuel, and 0.3 watt per square centimeter on CH 4 fuel in fuel cell mode. In steam electrolysis mode, a current density of >0.6 ampere per square centimeter with a Faradaic efficiency of >90% is achievable at 1.4 volt and 400°C. In addition, exceptional durability (>2000 hours) has been demonstrated, with a degradation rate of <0.01 millivolt per 100 hours in fuel cell mode at 400°C.

Science & Technology - Other Topics↗

Modeling In-Reactor Temperature Gradients in Lithium Aluminate Ceramic Pellets

In reactor thermal performance of lithium aluminate ceramic pellets are calculated to determine operating temperatures if internal components shift during irradiation. A 2D conduction model was setup to model this scenario with additional physics, including thermal expansion of components to reactor temperatures, creep down of the cladding due to differential pressure between the inside of the rod and reactor coolant system, and net radiation exchange between components. The non-linear coupling of the governing equations presented convergence challenges due to the very different effects from a small temperature change on the radiation vs radial and circumferential conduction equations. Initial temperature guesses for the multidimensional solution were provided from conservative 1D models simulating bounding scenarios. Convergence was greatly improved by taking small steps towards the root solutions and averaging with initial guesses. The final method robustly converged all 132 points at an axial plane after a few dozen iterations. The temperature results show that the additional physics have a secondary effect as the dominant heat transfer mechanism is radial conduction across the gas gap followed by circumferential conduction around components. Circumferential conduction in the lithium aluminate pellets is enhanced by the relatively high thermal conductivity of this ceramic.

Carstens, Nathan A.↗

Biocompatibility of a novel heat-treated and ceramic-coated magnesium alloy (Mg–1.2Zn–0.5Ca–0.5Mn) for resorbable skeletal fixation devices

Our recent exploration into the use of biodegradable metals and surface treatments resulting in sufficient strength for skeletal reconstruction applications has led to the need to test these devices’ cytotoxicity. More specifically, our group has developed a resorbable magnesium alloy, Mg–1.2Zn–0.5Ca–0.5Mn, that can be strengthened by heat treatment and coated with a ceramic layer offering time-certain resorption of a medical device. This in vitro study shows that these treatments do not result in cytotoxicity. Both heat-treated (HT) and HT + ceramic-coated (sol–gel) coupons demonstrated more than 70% viability. Thus, these processing steps are likely to be useful in producing biocompatible, resorbable implants that incorporate our Mg–1.2Zn–0.5Ca–0.5Mn alloy.

36 MATERIALS SCIENCE↗

Preparation and electrical properties of the new lead-free (1 &minus; x )Bi 0.5 Na 0.5 TiO 3 &ndash; x Ba(Ni 1/3 Nb 2/3 )O 3 piezoelectric ceramics

A new lead-free piezoelectric ceramics of (1 - x)Bi 0.5 Na 0.5 TiO 3–x Ba(Ni 1/3 Nb 2/3 )O 3 (BNT–BNN) (x = 0.0–0.07) have been prepared by a conventional solid reaction method. Their structures and electric properties have been investigated systematically. A pure perovskite phase can be formed in x ≤ 0.06. By the introduction of Ba(Ni 1/3 Nb 2/3 )O 3 , the ceramics exhibit a lower coercive field EC. Composition for x = 0.02 shows optimal piezoelectric properties, with the piezoelectric coefficient d 33 = 121 pC/N. Temperature dependent P(E) loops and S(E) curves of 0.98BNT–0.02BNN indicate that the phase transition from the ferroelectric to antiferroelectric takes place over a very wide temperature range from 75 to 150°C.

36 MATERIALS SCIENCE↗

Fracture Toughness Prediction for MWCNT Reinforced Ceramics

This report describes the development of a micromechanics model to predict fracture toughness of multiwall carbon nanotube (MWCNT) reinforced ceramic composites to guide future experimental work for this project. The modeling work described in this report includes (i) prediction of elastic properties, (ii) development of a mechanistic damage model accounting for matrix cracking to predict the composite nonlinear stress/strain response to tensile loading to failure, and (iii) application of this damage model in a modified boundary layer (MBL) analysis using ABAQUS to predict fracture toughness and crack resistance behavior (R-curves) for ceramic materials containing MWCNTs at various volume fractions.

36 MATERIALS SCIENCE↗

Online, In-Situ Monitoring Combustion Turbines Using Wireless Passive Ceramic Sensors

The overall objective of this project is to develop high-temperature wireless passive ceramic sensors for online, real-time monitoring combustion turbines. During this project period, we have successfully demonstrated temperature sensors up to 1300°C and pressure sensors up to 800°C. The temperature sensor is based on a high-Q-factor dielectric resonator and the pressure sensor utilizes the evanescent-mode cavity to realize a pressure-sensitive high-Q-factor resonator. Both sensors are efficiently integrated with a compact antenna. These sensors are wirelessly interrogated. The resonant frequency change corresponding to either temperature or pressure can be identified using a time-domain gating technique. The sensors realized in this project can survive harsh environments characterized by high temperatures (>1000°C) and corrosive gases, owing to the excellent material properties of polymer-derived ceramics (PDCs) developed at University of Central Florida. It is anticipated that this work will significantly advance the capability of high-temperature sensor technologies and be of a great benefit to turbine industry and their customers.

47 OTHER INSTRUMENTATION↗

Ceramic Waste Form Data Package

The purpose of this data package is to provide information about simulated crystalline waste forms that can be used to select an appropriate composition for a Cold Crucible Induction Melter (CCIM) proof of principle demonstration. Melt processing, viscosity, electrical conductivity, and thermal analysis information was collected to assess the ability of two potential candidate ceramic compositions to be processed in the Idaho National Laboratory (INL) CCIM and to guide processing parameters for the CCIM operation. Given uncertainties in the CCIM capabilities to reach certain temperatures throughout the system, one waste form designated 'Fe-MP' was designed towards enabling processing and another, designated 'CAF-5%TM-MP' was designed towards optimized microstructure. Melt processing studies confirmed both compositions could be poured from a crucible at 1600°C although the CAF-5%TM-MP composition froze before pouring was complete due to rapid crystallization (upon cooling). X-ray diffraction measurements confirmed the crystalline nature and phase assemblages of the compositions. The kinetics of melting and crystallization appeared to vary significantly between the compositions. Impedance spectroscopy results indicated the electrical conductivity is acceptable with respect to processing in the CCIM. The success of processing either ceramic composition will depend on the thermal profiles throughout the CCIM. In particular, the working temperature of the pour spout relative to the bulk melter which can approach 1700°C. The Fe-MP composition is recommended to demonstrate proof of principle for crystalline simulated waste forms considering the current configuration of INL's CCIM. If proposed modifications to the CCIM can maintain a nominal temperature of 1600°C throughout the melter, drain, and pour spout, then the CAF-5%TM-MP composition should be considered for a proof of principle demonstration.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Atomistic Structure, Strength, and Kinetic Properties of Intergranular Films in Ceramics

Intergranular films (IGFs) present in polycrystalline oxide and nitride ceramics provide an excellent example of nanoconfined glasses that occupy only a small volume percentage of the bulk ceramic, but can significantly influence various mechanical, thermal, chemical, and optical properties. By employing molecular dynamics computer simulations, we have been able to predict structures and the locations of atoms at the crystal/IGF interface that were subsequently verified with the newest electron microscopies. Modification of the chemistry of the crystal surface in the simulations provided the necessary mechanism for adsorption of specific rare earth ions from the IGF in the liquid state to the crystal surface. Such results had eluded other computational approaches such as ab-initio calculations because of the need to include not only the modified chemistry of the crystal surfaces but also an accurate description of the adjoining glassy IGF. This segregation of certain ions from the IGF to the crystal caused changes in the local chemistry of the IGF that affected fracture behavior in the simulations. Additional work with the rare earth ions La and Lu in the silicon oxynitride IGFs showed the mechanisms for their different affects on crystal growth, even though both types of ions are seen adhering to a bounding crystal surface that would normally imply equivalent affects on grain growth.

36 MATERIALS SCIENCE↗

Alternative High-Performance Ceramic Waste Forms

This final report (M5NU-12-NY-AU # 0202-0410) summarizes the results of the project titled “Alternative High-Performance Ceramic Waste Forms,” funded in FY12 by the Nuclear Energy University Program (NEUP Project # 12-3809) being led by Alfred University in collaboration with Savannah River National Laboratory (SRNL). The overall focus of the project is to advance fundamental understanding of crystalline ceramic waste forms and to demonstrate their viability as alternative waste forms to borosilicate glasses. We processed single- and multiphase hollandite waste forms based on simulated waste streams compositions provided by SRNL based on the advanced fuel cycle initiative (AFCI) aqueous separation process developed in the Fuel Cycle Research and Development (FCR&D). For multiphase simulated waste forms, oxide and carbonate precursors were mixed together via ball milling with deionized water using zirconia media in a polyethylene jar for 2 h. The slurry was dried overnight and then separated from the media. The blended powders were then subjected to melting or spark plasma sintering (SPS) processes. Microstructural evolution and phase assemblages of these samples were studied using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion analysis of x-rays (EDAX), wavelength dispersive spectrometry (WDS), transmission electron spectroscopy (TEM), selective area x-ray diffraction (SAXD), and electron backscatter diffraction (EBSD). These results showed that the processing methods have significant effect on the microstructure and thus the performance of these waste forms. The Ce substitution into zirconolite and pyrochlore materials was investigated using a combination of experimental (in situ XRD and x-ray absorption near edge structure (XANES)) and modeling techniques to study these single phases independently. In zirconolite materials, a transition from the 2M to the 4M polymorph was observed with increasing Ce content. The resulting powders were consolidated via SPS. Ce was reduced to the trivalent oxidation state and the zirconolite was converted into undesirable perovskite. The zirconolite polymorphs found in the synthesized powders were recovered after a post-SPS heat treatment in air. These results demonstrated the potential of processing in controlling the phase assemblage in these waste forms. Hollandites with Cr 3+ trivalent cations were identified as potential hosts for Cs immobilization and are being investigated for Cs retention properties. Series of compositions Ba 1.15-x Cs 2x Cr 2.3 Ti 5.7 O 16 , with increasing Cs loadings, were prepared by sol-gel process and characterized for structural parameters. Structural characterization was performed by a combination of powder XRD and neutron powder diffraction. Phase pure hollandite adapting monoclinic symmetry (I2/m) was observed for 0 ≤ x ≤ 0.55. These results were used to develop a new structural model to interpret Cs immobilization in these hollandites. Performance of these waste forms were evaluated for chemical durability and radiation resistance. Product consistency testing (PCT) and vapor hydration testing (VHT) were used for testing of chemical durability. Radiation resistance was tested using He + ions to simulate $\alpha$ particles and heavy ions such as Au 3+ to simulate a recoil. These results showed that these waste forms were chemically durable. The waste forms also amorphized to various degrees on exposure to simulated radiation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of the ICET Test Stand to Assess the Performance of a Range of Ceramic Media Filter Elements in Support of ASME AG-1 Subsection FO

High Efficiency Particulate Air (HEPA) filters are defined as extended-medium, dry-type filters with: (1) a minimum particle removal efficiency of no less than 99.97 percent for 0.3 micrometer particles, (2) a maximum, clean resistance of 1.0 inch water column (in. WC) when operated at 1,000 cubic feet per minute (CFM), and (3) a rigid casing that extends the full depth of the medium. Specifically, ceramic media HEPA filters provide better performance at elevated temperatures, are moisture resistant and nonflammable, can perform their function if wetted and exposed to greater pressures, and can be cleaned and reused. This paper describes the modification and design of a large scale test stand which properly evaluates the filtration characteristics of a range of ceramic media filters challenged with a nuclear aerosol agent in order to develop Section FO of ASME AG-1.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Commercialization of Ultra-Hard Ceramics for Cutting Tools Final Report CRADA No. TC0279.0

This was a collaborative effort between Lawrence Livermore National Security, LLC as manager and operator of Lawrence Livermore National Laboratory (LLNL) and Greenleaf Corporation (Greenleaf) to develop the technology for forming unique precursor nano-powders process that can be consolidated into ceramic products for industry. LLNL researchers have developed a solgel process for forming nano-ceramic powders. The nano powders are highly tailorable, allowing the explicit design of desired properties that lead to ultra hard materials with fine grain size. The present CRADA would allow the two parties to continue the development of the sol-gel process and the consolidation process in order to develop an industrially sound process for the manufacture of these ultra-hard materials.

36 MATERIALS SCIENCE↗

High-pressure polymorphism of two high-strength ceramics: Boron carbide (B4C) and silicon carbide (SiC)

We have determined the lattice-level structure of two high-strength, technologically important ceramic materials under shock wave compression. For decades, laboratory shock wave studies have provided crucial information on the dynamic response of many types of materials. However, previous studies were limited to continuum-level information only. By combining laser compression with pulsed X-ray diffraction we are able to obtain in situ structural information on these materials for the first time. Silicon carbide (SiC) and boron carbide (B4C) are two high-strength ceramics with many technical applications including debris shielding, armoring, and coating. We have carried out Xray diffraction measurements of the structure of SiC and B4C under shock compression to 185 and 300 GPa, respectively. Experiments were performed at the Matter in Extreme Conditions beamline of the Linac Coherent Light Source (LCLS). At LCLS, shock waves are driven into the sample using a high powered laser with approximately 10 nanosecond pulse length. The sample is probed with X-rays from the LCLS free electron laser and diffraction is recorded by x-ray detectors. By varying the delay between the laser and the x-ray probe, the sample can be studied at various times relative to the shock wave entering the sample. The diffraction data have been analyzed to determine the crystal structures, lattice parameters, density, and crystallographic texture as a function of pressure and loading time.

36 MATERIALS SCIENCE↗

Understanding and Controlling Toughening Mechanisms in Nanotube Reinforced Ceramic Coatings

Research in this program is designed to understand mechanical behavior, particularly fracture toughness, in ceramics that are reinforced with carbon nanotubes (CNTs). In the past four years, emphasis was placed on: Synthesizing and characterizing ceramic nanocomposite materials reinforced with both multiwall carbon nanotubes (MWNTs) and single wall nanotubes (SWNTs); and Implementation and analysis of in situ mechanical testing methods to better understand and engineer the critical CNT/ceramic interfaces.

36 MATERIALS SCIENCE↗

Phase separation and crystallization of complex borosilicate melts for glass-ceramic waste forms

Waste loadings of reprocessed spent nuclear fuel vitrified into borosilicate glass can be increased by precipitating environmentally stable phases concentrated with waste components in a chemically stable glass matrix. The principal objective of this study was to characterize the development of crystalline powellite (CaMoO 4 and related phases) and oxyapatite (Ca 2 LN 8 Si 6 O 26 ) in borosilicate glass-ceramics and to determine how the formation of those phases affected its chemical durability. Borosilicate glasses provided by PNNL were re-melted and quenched at rates from over 300°C/s to ~0.05°C/s. Isothermal heat treatment experiments were conducted by quenching melts in a molten tin bath at various temperatures, holding for periods of time, and then quenching in a water bath. Analytical electron microscopy and x-ray diffraction provided information about the kinetics of the phase separation and crystallization processes responsible for microstructural development. Powellite and oxyapatite crystals formed during slower quench rates and longer isothermal times, and time-temperature-transformation (TTT) diagrams were developed from the latter experiments. A hot thermocouple test (HTT) system was built to rapidly quench melts and hold them at set times to provide supplementary TTT information, but that system was not as sensitive to the phase transformations as other tests. Corrosion tests were performed to understand how the individual phases in the glass-ceramic affect its overall chemical durability. Product consistency tests, performed at Missouri S&T and at Savannah River National Lab, provided release rates of major elements from samples as a function of cooling rate, and atomic force microscopy and profilometry measurements of surface topology determined the relative corrosion rates of the residual glass and oxyapatite phases. Faster dissolution rates were measured from samples cooled more slowly and these were explained by the greater fractions of B 2 O 3 in the residual glass phase after the formation of oxyapatite and powellite. Oxyapatite was found to be more durable than the residual glass.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗