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At least 271 records · Page 15

The Influence of Residual Copper Catalyst on the Polymer-to-Ceramic Conversion of a Click-Derived Polycarbosilane

Preceramic polymers (PCPs) are a key class of materials for the preparation of advanced ceramic components. Following conventional polymer processing and subsequent pyrolysis, polymer-derived ceramic (PDC) fibers, monoliths, and composites offer novel engineering opportunities for aerospace applications. Despite the rapidly emerging commercial applications of PDCs, many basic scientific questions remain regarding the structural transformation of the polymer to the final ceramic and how processing variables affect PDC materials properties. PCPs prepared using a mild and scalable copper (Cu) catalyzed azide/alkyne “click” reaction have been demonstrated as a unique class of material that can bind with transition metals, ultimately producing ultrahigh temperature ceramics (UHTCs) upon pyrolysis. Unexpectedly, it was found that the removal of residual Cu catalyst from a model click-derived polycarbosilane PCP significantly reduced the ceramic yield during pyrolysis. Herein, we report the influence of Cu impurities on polycarbosilane-derived SiC ceramics and present a mechanistic understanding of the unintended role of Cu in the polymer-to-ceramic conversion process. Synchrotron-based scattering and spectroscopy methods were implemented to track the evolution of different atomic species and local structures as well as the influence of Cu toward atomic-scale structures in the final ceramics. It was determined that Cu impurities catalyze the formation of silicon carbide through the formation of an intermediate molten copper/copper silicide, ultimately increasing the ceramic yield. Overall, this contribution highlights the need to carefully assess the interplay between the chemistries needed for PCP synthesis and their potential influence on final PDCs following processing.

Ponder, Jr., James F. [Air Force Research Laborato↗

Plasma-Spraying Ceramics Onto Smooth Metallic Substrates

In fabrication process, plasma-sprayed ceramic coats bonded strongly to smooth metallic surfaces. Principal use of such coats in protecting metal parts in hot-gas paths of advanced gas turbine engines. Process consists of application of initial thin layer of ceramic on smooth surface by low-pressure-plasma spraying followed by application of layer of conventional, low-thermal-conductivity atmospheric-pressure plasma-sprayed ceramic.

Miller, Robert A.↗

Method for improving the performance of oxidizable ceramic materials in oxidizing environments

Improved adhesion of thermal barrier coatings to nonmetallic substrates using a dense layer of ceramic on an underlying nonmetallic substrate that includes at least one oxidizable component. The improved adhesion occurs because the application of the dense ceramic layer forms a diffusion barrier for oxygen. This diffusion barrier prevents the oxidizable component of the substrate from decomposing. The present invention applies ceramic by a process that deposits a relatively thick and dense ceramic layer on the underlying substrate. The formation of the dense layer of ceramic avoids the problem of void formation associated with ceramic formation by most prior art thermal decomposition processes. The formation of voids has been associated with premature spalling of thermal barrier layers and other protective layers applied to substrates.

Nagaraj, Bangalore A.↗

Formation mechanism and characteristics of lanthanum-doped BaTiO{sub 3} powders and ceramics prepared by the sol–gel process

Pure and lanthanum-doped barium titanate nanopowders described by two different formulae, as Ba{sub 1−x}La{sub x}TiO{sub 3}, for lower La concentrations (0 ≤ x ≤ 0.005) and Ba{sub 1−x}La{sub x}Ti{sub 1−x/4}O{sub 3} for higher La concentration (x = 0.025) were prepared by an alkoxide sol–gel method. Single phase compositions were obtained after annealing at 900 °C for 2 h, in air. The increase of the lanthanum content causes structural and morphological changes in the oxide powders, including the evolution of the unit cell from tetragonal toward a cubic symmetry, the particle size decrease and a higher aggregation tendency. SEM investigations of the ceramics sintered at 1300 °C for 4 h indicate significant changes of the microstructural features (strong decrease of the average grain size and increase of the intergranular porosity) with the raise of La amount. Lanthanum addition to barium titanate prepared by sol–gel induces a more significant shift of the Curie temperature toward lower values, than that one reported in literature for ceramics of similar compositions, but processed by the conventional solid state method. The compositions with smaller La amount (x ≤ 0.005) show semiconducting properties at room temperature and high relative dielectric permittivity values, while the undoped ceramics and those doped with higher La content (x = 0.025) are good dielectrics. The ceramic with x = 0.025 exhibits acceptable low losses, a very diffuse ferroelectric–paraelectric transition and Curie temperature closed to the room temperature, being thus susceptible for high tunability applications. - Highlights: • Ba{sub 1−x}La{sub x}TiO{sub 3} (x ≤ 0.005) and Ba{sub 1−x}La{sub x}Ti{sub 1−x/4}O{sub 3} (x = 0.025) were prepared by sol–gel. • Ceramics with x < 0.5 exhibit semiconductor and high dielectric properties. • Ceramic with x = 0.025 exhibits acceptable low losses and diffuse phase transition.

36 MATERIALS SCIENCE↗

Extension of a noninteractive reliability model for ceramic matrix composites

Developments in the processing of high temperature ceramic composites demand innovative and progressive design protocols that adequately predict the thermal and mechanical behavior of these materials. The focus here is the extension of a reliability model for orthotropic ceramic composites. The approach chosen to describe failures leads to a noninteractive formulation of reliability that is phenomenological. This particular criterion, which was constructed using tensorial invariant theory, allows six potential failure modes to emerge.

Duffy, Stephen F.↗

Radiation damage of hollandite in multiphase ceramic waste forms

Radiation damage was simulated in multiphase titanate-based ceramic waste forms using an ion accelerator to generate high energy alpha particles (He + ) and an ion implanter to generate 7 MeV gold (Au 3+ ) particles. X-ray diffraction and transmission electron microscopy were used to characterize the damaged surfaces and nearby regions. Simulated multiphase ceramic waste forms were prepared using two processing methods: spark plasma sintering and melt-processing. Both processing methods produced ceramics with similar phase assemblages consisting of hollandite-, zirconolite/pyrochlore-, and perovskite- type phases. The measured heavy ion (Au 3+ ) penetration depth was less in spark plasma sintered samples than in melt-processed samples. Furthermore, structural breakdown of the hollandite phase occurred under He + irradiation indicated by the presence of x-ray diffraction peaks belonging to TiO 2 , BaTiO 5 , and other hollandite related phases (Ba 2 Ti 9 O 20 ). The composition of the constituent hollandite phase affected the extent of damage induced by Au 3+ ions.

36 MATERIALS SCIENCE↗

Nonaqueous slip casting of high temperature ceramic superconductors using an investment casting technique

A process for slip casting ceramic articles that does not employ parting agents and affords the casting of complete, detailed, precision articles that do not possess parting lines is presented. This process is especially useful for high temperature superconductors and water-sensitive ceramics. A wax pattern for a shell mold is provided, and an aqueous mixture of a calcium sulfate-bonded investment material is applied as a coating to the wax pattern. The coated wax pattern is then dried, followed by curing to vaporize the wax pattern and leave a shell mold of the calcium sulfate-bonded investment material. The shell mold is cooled to room temperature, and a ceramic slip, created by dispersing a ceramic powder in an organic liquid, is poured therein. After a ceramic shell of desired thickness or a solid article has set up in the shell mold, excess ceramic slip is poured out. The shell mold is misted with water and peeled away from the ceramic article, after which the ceramic is fired to provide a complete, detailed, precision, high temperature superconductive ceramic article without parting lines. The casting technique may take place in the presence of a magnetic field to orient the ceramic powders during the casting process.

Hooker, Matthew W.↗

Method of depositing a coating on Si-based ceramic composites

A process of depositing a coating system suitable for use as an environmental barrier coating on various substrate materials, particularly those containing silicon and intended for high temperature applications such as the hostile thermal environment of a gas turbine engine. The process comprises depositing a first coating layer containing mullite, and preferably a second coating layer of an alkaline earth aluminosilicate, such as barium-strontium-aluminosilicate (BSAS), by thermal spraying while maintaining the substrate at a temperature of 800.degree. C. or less, preferably 500.degree. C. or less, by which a substantially crack-free coating system is produced with desirable mechanical integrity.

Wang, Hongyu↗

Lightweight ceramic insulation and method

A process is disclosed for manufacturing a low density ceramic powder which can be formed to make a lightweight material for insulation or other construction. The ceramic product made from the process has a final density of less than 25 to about 1 percent of the theoretical weight of the ceramic powder. The ceramic product is lightweight and can be made to withstand high temperatures greater than 1400 C.

Green, David J.↗

Processing and Characterization of Basalt Fiber Reinforced Ceramic Composites for High Temperature Applications Using Polymer Precursors

The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, which allows a shape to be formed prior to the cure, and is then pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The two PDCs used in this development are polysiloxane and polycarbosilane. Basalt fibers are used for the reinforcement in the composite system. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in composites. Continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material.

High Temperature Composites↗

3D printing of ceramics: Advantages, challenges, applications, and perspectives

Abstract 3D printing (3DP) technologies have transformed the processing of advanced ceramics for small‐scale and custom designs during the past three decades. Simple and complex parts are designed and manufactured using 3DP technologies for structural, piezoelectric, and biomedical applications. Manufacturing simple or complex geometries or one‐of‐a‐kind components without part‐specific tooling saves significant time and creates new applications for advanced ceramic materials. Although development and innovations in 3DP of ceramics are far behind compared with metals or polymers, with the availability of different commercial machines in recent years for 3DP of ceramics, exponential growth is expected in this field in the coming decade. This article details various 3DP technologies for advanced ceramic materials, their advantages and challenges for manufacturing parts for various applications, and perspectives on future directions. We envision this work will be helpful to advanced ceramic researchers in industry and academia who are using different 3DP processes in the coming days.

36 MATERIALS SCIENCE↗

Nonlinear fracture of concrete and ceramics

The nonlinear fracture process zones in an impacted unnotched concrete bend specimen, a prenotched ceramic bend specimen, and an unnotched ceramic/ceramic composite bend specimen were estimated through hybrid experimental numerical analysis. Aggregate bridging in concrete, particulate bridging in ceramics, and fiber bridging in ceramic/ceramic composite are modeled by Barenblatt-type cohesive zones which are incorporated into the finite-element models of the bend specimens. Both generation and propagation analyses are used to estimate the distribution of crack closure stresses in the nonlinear fracture process zones. The finite-element models are then used to simulate fracture tests consisting of rapid crack propagation in an impacted concrete bend specimen, and stable crack growth and strain softening in a ceramic and ceramic/ceramic composite bend specimens.

Kobayashi, Albert S.↗

Advanced Turbine Technology Applications Project (ATTAP)

Reports technical effort by AlliedSignal Engines in sixth year of DOE/NASA funded project. Topics include: gas turbine engine design modifications of production APU to incorporate ceramic components; fabrication and processing of silicon nitride blades and nozzles; component and engine testing; and refinement and development of critical ceramics technologies, including: hot corrosion testing and environmental life predictive model; advanced NDE methods for internal flaws in ceramic components; and improved carbon pulverization modeling during impact. ATTAP project is oriented toward developing high-risk technology of ceramic structural component design and fabrication to carry forward to commercial production by 'bridging the gap' between structural ceramics in the laboratory and near-term commercial heat engine application. Current ATTAP project goal is to support accelerated commercialization of advanced, high-temperature engines for hybrid vehicles and other applications. Project objectives are to provide essential and substantial early field experience demonstrating ceramic component reliability and durability in modified, available, gas turbine engine applications; and to scale-up and improve manufacturing processes of ceramic turbine engine components and demonstrate application of these processes in the production environment.

Source record↗

Optimization of the Processing Parameters of High Temperature Superconducting Glass-Ceramics: Center Director's Discretionary Fund Final Report

A number of promising glass forming compositions of high Tc superconducting Ba-Sr-Ca-Cu-O (BSCCO) materials were evaluated for their glass-ceramic crystallization ability. The BSCCO ceramics belonging to the class of superconductors in the Ba-Sr-Ca-Cu-O system were the focus of this study. By first forming the superconducting material as a glass, subsequent devitrification into the crystalline (glass-ceramic) superconductor can be performed by thermal processing of the glass preform body. Glass formability and phase formation were determined by a variety of methods in another related study. This study focused on the nucleation and crystallization of the materials. Thermal analysis during rapid cooling aids in the evaluation of nucleation and crystallization behavior. Melt viscosity is used to predict glass formation ability.

Ethridge, E. C.↗

Bioinspired nacre-like alumina with a bulk-metallic glass-forming alloy as a compliant phase

Bioinspired ceramics with micron-scale ceramic "bricks" bonded by a metallic "mortar" are projected to result in higher strength and toughness ceramics, but their processing is challenging as metals do not typically wet ceramics. To resolve this issue, we made alumina structures using rapid pressureless infiltration of a zirconium-based bulk-metallic glass mortar that reactively wets the surface of freeze-cast alumina preforms. The mechanical properties of the resulting Al 2 O 3 with a glass-forming compliant-phase change with infiltration temperature and ceramic content, leading to a trade-off between flexural strength (varying from 89 to 800 MPa) and fracture toughness (varying from 4 to more than 9 MPa·m ½ ). The high toughness levels are attributed to brick pull-out and crack deflection along the ceramic/metal interfaces. Since these mechanisms are enabled by interfacial failure rather than failure within the metallic mortar, the potential for optimizing these bioinspired materials for damage tolerance has still not been fully realized.

36 MATERIALS SCIENCE↗

Glass-Ceramic Material Modeling

Glass-ceramics are a unique class of materials in which the growth of a ceramic phase(s) may be induced in an inorganic glass resulting in a microstructurally heterogeneous material with both glass and ceramic phases. This specialized processing is often referred to as "ceramming''. A wide variety of such materials have been developed through the use of different initial glass compositions and thermomechanical processing routes and that have enabled applications in dentistry, consumer kitchenware, and telescopes mirrors. These materials may also exhibit large apparent coefficients of thermal expansion making them attractive for consideration in glass-ceramic seals. These large apparent coefficients of thermal expansion often arise from silica polymorphs, such as cristobalite, undergoing a solid-to-solid phase transformations producing additional non-linearity in the effective material response.

36 MATERIALS SCIENCE↗

Processing Methods Established To Fabricate Porous Oxide Ceramic Spheres for Thermal Barrier Coating Applications

As gas turbine technology advances, the demand for efficient engines and emission reduction requires a further increase in operating temperatures, but combustion temperatures are currently limited by the temperature capability of the engine components. The existing thermal barrier coating (TBC) technology does not provide sufficient thermal load reduction at a 3000 F (1649 C) operating condition. Advancement in thermal barrier coating technology is needed to meet this aggressive goal. One concept for improving thermal barrier coating effectiveness is to design coating systems that incorporate a layer that reflects or scatters photon radiation. This can be achieved by using porous structures. The refractive index mismatch between the solid and pore, the pore size, and the pore density can be engineered to efficiently scatter photon radiation. Under NASA s Ultra-Efficient Engine Technology (UEET) Program, processing methods to fabricate porous ceramic spheres suitable for scattering photon radiation at elevated temperatures have been established. A straightforward templating process was developed at the NASA Glenn Research Center that requires no special processing equipment. The template was used to define particle shape, particle size, and pore size. Spherical organic cation exchange resins were used as a structure-directing template. The cation exchange resins have dual template capabilities that can produce different pore architectures. This process can be used to fabricate both metal oxide and metal carbide spheres.

Dynys, Frederick W.↗

Rare-earth doped transparent ceramics for spectral filtering and quantum information processing

Homogeneous linewidths below 10 kHz are reported for the first time in high-quality Eu{sup 3+} doped Y {sub 2}O{sub 3} transparent ceramics. This result is obtained on the {sup 7}F{sub 0}→{sup 5}D{sub 0} transition in Eu{sup 3+} doped Y {sub 2}O{sub 3} ceramics and corresponds to an improvement of nearly one order of magnitude compared to previously reported values in transparent ceramics. Furthermore, we observed spectral hole lifetimes of ∼15 min that are long enough to enable efficient optical pumping of the nuclear hyperfine levels. Additionally, different Eu{sup 3+} concentrations (up to 1.0%) were studied, resulting in an increase of up to a factor of three in the peak absorption coefficient. These results suggest that transparent ceramics can be useful in applications where narrow and deep spectral holes can be burned into highly absorbing lines, such as quantum information processing and spectral filtering.

36 MATERIALS SCIENCE↗