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At least 37 records · Page 2

Vapor Infiltration Synthesis of Indium Sulfide Magic Size Cluster

The energetically favorable formation of atomically precise clusters, known as magic size clusters, in the solution phase enables a precision nanoscale synthesis with exquisite uniformity. Here, we report the synthesis of magic size clusters via vapor infiltration of atomic layer deposition precursors directly in a polymer thin film. Sequential infiltration of trimethylindium vapor and hydrogen sulfide gas into poly(methyl methacrylate) leads to the formation of clusters with uniform properties consistent with a magic size cluster-In 6 S 6 (CH 3 ) 6 . While an increase in cluster size might be expected with additional sequential infiltration cycles of the reactive In and S precursors, uniform properties consistent with magic size clusters form in multiple polymers under a range of processing conditions. Ultraviolet-visible absorption spectra of In 6 S 6 (CH 3 ) 6 are largely independent of the number of sequential infiltration cycles and exhibit air stability, both of which are attributed to an energetically favorable synthetic pathway that is evaluated with density functional theory.

atomic layer deposition

Simplified, Infiltration-free Ceramic Matrix Composite Manufacturing

Manufacturing of ceramic matrix composites (CMCs) with carbon fiber and carbon matrix includes a time- and labor-intensive ceramic infiltration step that is responsible for more than half of the total manufacturing cost. To make CMCs cost-competitive in price-sensitive markets, like concentrated solar power, it is essential to develop a CMC manufacturing process that skips the ceramic infiltration process. In this work, we will show how a high-char-yield preceramic resin can eliminate the infiltration step while maintaining material density and evaluate the technoeconomic impact of our CMC manufacturing process. Here, we monitor both morphology and porosity to determine the quality of CMCs made with different preceramic resins and evaluate the impact of polymer infiltration and pyrolyzing cycles.

36 MATERIALS SCIENCE

Infiltrated electrodes for metal supported solid oxide electrolysis cells

Metal-supported solid oxide cells (MSOCs) are an alternative to conventional solid oxide cells (SOCs) based on ceramic cermets, offering lower material costs and higher operational flexibility. In this study symmetric MSOCs with infiltrated electrodes are explored for steam electrolysis operation to understand the underlying operation and degradation principles and suggest a direction for future MSOCs development. Two different fuel electrode backbones are used: an electronically-conductive lanthanum strontium co-doped iron nickel titanate (LSFNT) infiltrated with cerium-gadolinium oxide (CGO), or an ionic conductive zirconia based backbone (10ScYSZ) infiltrated with Ni:CGO. At the oxygen side, the backbone is 10ScYSZ, which is infiltrated with lanthanum-strontium co-doped cobalt oxide (LSC), or praseodymium oxide as cobalt-free alternative for comparison. This study suggests that the backbone electronic conductivity is key for good electrochemical performance as well as for boosting cell durability. Highly electronically conductive nanoparticles, especially nickel, were observed to irreversibly agglomerate driven by thermal conditions, whereas CGO proved to be a very stable electrocatalyst. At the fuel side, CGO (LSFNT) electrode showed lower ASR and degradation rate than Ni:CGO(ScYSZ) configuration with measured values of 0.50 Ω cm2 and 11 %/1000 h (at 0.60 A/cm2), and 0.70 Ω cm2 and 26 %/1000 h (at 0.50 A/cm2) at 1.30 V, respectively (700 °C, 50 % steam in hydrogen at the fuel side and air at the oxygen electrode side, LSC(ScYSZ) oxygen electrode).

25 ENERGY STORAGE

Mechanism of Vapor-Phase Infiltration of Organometallic Hf in Poly(Methyl Methacrylate) for Hybrid Resist Applications

Inorganic–organic hybrid thin films synthesized by vapor-phase infiltration (VPI) of metal oxides into organic photoresists, such as poly(methyl methacrylate) (PMMA), have recently demonstrated their utility in extreme ultraviolet lithography, critical for angstrom-era semiconductor device miniaturization. Hafnium oxide infiltration has been reported recently for this purpose, but its detailed VPI mechanism has remained largely unexplored. In this study, we investigated the VPI characteristics and mechanisms of tetrakis(dimethylamido)hafnium (TDMAHf)─the hafnium precursor predominantly used for VPI in the field─into PMMA and examined its impact on electron-beam lithography (EBL) exposure behavior. VPI was performed at temperatures ranging from 85 to 150 °C, with chemical interactions characterized using infrared reflection-absorption spectroscopy, and resist patterning performance was evaluated through EBL dose-sensitivity assessments. The results indicate that TDMAHf forms a reversible adduct with PMMA at temperatures up to 120 °C, whereas at 150 °C, covalent bond formation occurs, most likely via dealkylation that leads to acetate formation. EBL studies reveal that resist sensitivity is influenced by both infiltration temperature and developer selection, with aqueous isopropyl alcohol development demonstrating enhanced sensitivity compared to organic solvent-based development. The optimized infiltration protocol at 120 °C ensures a uniform inorganic distribution without compromising resist dissolution. These findings not only help refine hybrid resist patterning performance but also offer insights potentially applicable to the VPI of other homoleptic metal-amide organometallic VPI precursors that include TDMA ligands.

36 MATERIALS SCIENCE

Studies on the reactive melt infiltration of silicon and silicon-molybdenum alloys in porous carbon

Investigations on the reactive melt infiltration of silicon and silicon-1.7 and 3.2 at percent molybdenum alloys into porous carbon preforms have been carried out by process modeling, differential thermal analysis (DTA) and melt infiltration experiments. These results indicate that the initial pore volume fraction of the porous carbon preform is a critical parameter in determining the final composition of the raction-formed silicon carbide and other residual phases. The pore size of the carbon preform is very detrimental to the exotherm temperatures due to liquid silicon-carbon reactions encountered during the reactive melt infiltration process. A possible mechanism for the liquid silicon-porous (glassy) carbon reaction has been proposed. The composition and microstructure of the reaction-formed silicon carbide has been discussed in terms of carbon preform microstructures, infiltration materials, and temperatures.

Singh, M.

Verification of a two-dimensional infiltration model for the resin transfer molding process

A two-dimensional finite element model for the infiltration of a dry textile preform by an injected resin was verified. The model, which is based on the finite element/control volume technique, determines the total infiltration time and the pressure increase at the mold inlet associated with the RTM process. Important input data for the model are the compaction and permeability behavior of the preform along with the kinetic and rheological behavior of the resin. The compaction behavior for several textile preforms was determined by experimental methods. A power law regression model was used to relate fiber volume fraction to the applied compaction pressure. Results showed a large increase in fiber volume fraction with the initial application of pressure. However, as the maximum fiber volume fraction was approached, the amount of compaction pressure required to decrease the porosity of the preform rapidly increased. Similarly, a power law regression model was used to relate permeability to the fiber volume fraction of the preform. Two methods were used to measure the permeability of the textile preform. The first, known as the steady state method, measures the permeability of a saturated preform under constant flow rate conditions. The second, denoted the advancing front method, determines the permeability of a dry preform to an infiltrating fluid. Water, corn oil, and an epoxy resin, Epon 815, were used to determine the effect of fluid type and viscosity on the steady state permeability behavior of the preform. Permeability values measured with the different fluids showed that fluid viscosity had no influence on the permeability behavior of 162 E-glass and TTI IM7/8HS preforms. Permeabilities measured from steady state and advancing front experiments for the warp direction of 162 E-glass fabric were similar. This behavior was noticed for tests conducted with corn oil and Epon 815. Comparable behavior was observed for the warp direction of the TTI IM7/8HS preform and corn oil. Mold filling and flow visualization experiments were performed to verify the analytical computer model. Frequency dependent electromagnetic sensors were used to monitor the resin flow front as a function of time. For the flow visualization tests, a video camera and high resolution tape recorder were used to record the experimental flow fronts. Comparisons between experimental and model predicted flow fronts agreed well for all tests. For the mold filling tests conducted at constant flow rate injection, the model was able to accurately predict the pressure increase at the mold inlet during the infiltration process. A kinetics model developed to predict the degree of cure as a function of time for the injected resin accurately calculated the increase in the degree of cure during the subsequent cure cycle.

Hammond, Vincent H.

Mathematical Analysis and Optimization of Infiltration Processes

A variety of infiltration techniques can be used to fabricate solid materials, particularly composites. In general these processes can be described with at least one time dependent partial differential equation describing the evolution of the solid phase, coupled to one or more partial differential equations describing mass transport through a porous structure. This paper presents a detailed mathematical analysis of a relatively simple set of equations which is used to describe chemical vapor infiltration. The results demonstrate that the process is controlled by only two parameters, alpha and beta. The optimization problem associated with minimizing the infiltration time is also considered. Allowing alpha and beta to vary with time leads to significant reductions in the infiltration time, compared with the conventional case where alpha and beta are treated as constants.

Chang, H.-C.

Mechanical Behavior and Analytical Modeling of Melt-Infiltrated SiC/SiC Woven Composite

The desirable properties in ceramic matrix composites (CMCs), such as high temperature strength, corrosion resistance, high toughness, low density, or good creep resistance have led to increased use of CMCs in high-speed engine structural components and structures that operate in extreme temperature and hostile aero-thermo-chemical environments. Ceramic matrix composites have been chosen for turbine material in the design of 21st century civil propulsion systems to achieve high fuel economy, improved reliability, extended life, and reduced cost. Most commercial CMCs are manufactured using a chemical vapor infiltration (CVI) process. However, a lower cost fabrication known as melt-infiltration process is also providing CMCs marked for use in hot sections of high-speed civil transports. Limited samples of a SiC/SiC melt-infiltrated woven composites are being investigated at room and elevated temperature below and above matrix cracking. These samples show graceful failure and toughness at room temperature with a reduction in strength and modulus at elevated temperatures. A generic finite element model is also being developed to predict monotonic and cyclic loading behavior of the woven composite. Use of the initial test data from the woven composite is being used for the development of the analytical model. This model is the first of a iterative process leading towards the development the model's capability to predict behavior at room and elevated temperature for monotonic and cyclic loading. The purpose of this paper is to report on the material and mechanical findings of the SiC/SiC melt-infiltrated woven composite and progress on the development of the finite element model.

Lang, J.

Stress-Dependent Matrix Cracking in 2D Woven SiC-Fiber Reinforced Melt-Infiltrated SiC Matrix Composites

The matrix cracking of a variety of SiC/SiC composites has been characterized for a wide range of constituent variation. These composites were fabricated by the 2-dimensional lay-up of 0/90 five-harness satin fabric consisting of Sylramic fiber tows that were then chemical vapor infiltrated (CVI) with BN, CVI with SiC, slurry infiltrated with SiC particles followed by molten infiltration of Si. The composites varied in number of plies, the number of tows per length, thickness, and the size of the tows. This resulted in composites with a fiber volume fraction in the loading direction that ranged from 0.12 to 0.20. Matrix cracking was monitored with modal acoustic emission in order to estimate the stress-dependent distribution of matrix cracks. It was found that the general matrix crack properties of this system could be fairly well characterized by assuming that no matrix cracks originated in the load-bearing fiber, interphase, chemical vapor infiltrated Sic tow-minicomposites, i.e., all matrix cracks originate in the 90 degree tow-minicomposites or the large unreinforced Sic-Si matrix regions. Also, it was determined that the larger tow size composites had a much narrower stress range for matrix cracking compared to the standard tow size composites.

Morscher, Gregory N.

Infiltrated carbon foam composites

An infiltrated carbon foam composite and method for making the composite is described. The infiltrated carbon foam composite may include a carbonized carbon aerogel in cells of a carbon foam body and a resin is infiltrated into the carbon foam body filling the cells of the carbon foam body and spaces around the carbonized carbon aerogel. The infiltrated carbon foam composites may be useful for mid-density ablative thermal protection systems.

Lucas, Rick D.

Sequential Infiltration Synthesis of Multinary Metal Oxides: The Role of Precursor Diffusion and Reactivity

Understanding volatile metal–organic precursor transport in polymer matrices during sequential infiltration synthesis (SIS) is critical to the design of hybrid materials of tailored composition and uniform structure. Here, we investigate the diffusion and reaction behavior of diethylzinc (DEZ) in poly(methyl methacrylate) (PMMA) matrices with variable indium and zinc incorporation. Unlike conventional SIS where precursors adduct or react directly with the polymer backbone, DEZ shows minimal interaction with PMMA. However, DEZ may interact strongly with In–OH or Zn–OH moieties that are previously incorporated into a PMMA thick film. Using spectroscopic ellipsometry, X-ray photoelectron spectroscopy depth profiling, and EDX line scans, we quantify Zn incorporation as a function of exposure time, polymer thickness, and previous infiltration steps. The Zn distribution evolves from surface-localized to deep within the ∼1 μm thick film with increasing DEZ exposures up to 30 min. A reaction-diffusion model incorporating a hindering factor to capture diffusivity decay due to product accumulation reproduces the Zn depth profile and yields physically meaningful parameters to guide future growth. Furthermore, this study provides a framework for interpreting metal–organic precursor infiltration behavior and highlights the utility of model-guided SIS process design.

diethylzinc

Modeling Microwave-Enhanced Chemical Vapor Infiltration Process for Preventing Premature Pore Closure

The chemical vapor infiltration (CVI) process involves infiltrating a porous preform with reacting gases that undergo chemical transformation at high temperatures to deposit the ceramic phase within the pores, ultimately leading to a dense composite. The conventional CVI process in composite manufacturing needs to follow an isothermal approach to minimize temperature differences between the external and internal surfaces of the preform, ensuring that reactive gases infiltrate internal pores before external surfaces seal. Here, this study addresses the challenge of premature pore closure in CVI processes through microwave heating. A frequency-domain microwave solver is developed in OpenFOAM to investigate volumetric heating mechanisms within the preform. Through numerical studies, we demonstrate the capability of microwave heating of creating an inside-out temperature inversion. This inversion accelerates reactions proximal to the preform center, effectively mitigating the risk of premature external pore closure and ensuring uniform densification. The results reveal a significant enhancement in temperature inversion when high-permittivity reflectors are incorporated to generate resonant waves. This microwave heating strategy is then coupled with high-fidelity direct numerical simulation (DNS) of reacting flow, enabling the analysis of resulting densification processes. The DNS includes detailed chemistry and realistic diffusion coefficients. The numerical results can be used to estimate the impact of microwave-induced temperature inversion on densification in productions.

42 ENGINEERING

Development of lightweight aluminum compression panels reinforced by boron-epoxy infiltrated extrusions

Analytical and experimental studies were performed to evaluate the structural efficiencies afforded by the selective reinforcement of conventional aluminum compression panels with unidirectional boron epoxy composite materials. A unique approach for selective reinforcement was utilized called boron/epoxy infiltration. This technique uses extruded metal sections with preformed hollow voids into which unidirectional boron filaments are drawn and subsequently infiltrated with resin to form an integral part. Simplified analytical models were developed to investigate the behavior of stiffener webs with reinforced flanges. Theoretical results are presented demonstrating the effects of transverse shear, of the reinforcement, flange eccentricity and torsional stiffness in such construction. A series of 55 tests were conducted on boron-infiltrated rods and extruded structural sections.

Roy, P. A.

A model for estimating time-variant rainfall infiltration as a function of antecedent surface moisture and hydrologic soil type

Recent research indicates that the use of remote sensing techniques for the measurement of near surface soil moisture could be practical in the not too distant future. Other research shows that infiltration rates, especially for average or frequent rainfall events, are extremely sensitive to the proper definition and consideration of the role of the soil moisture at the beginning of the rainfall. Thus, it is important that an easy to use, but theoretically sound, rainfall infiltration model be available if the anticipated remotely sensed soil moisture data is to be optimally utilized for hydrologic simulation. A series of numerical experiments with the Richards' equation for an array of conditions anticipated in watershed hydrology were used to develop functional relationships that describe temporal infiltration rates as a function of soil type and initial moisture conditions.

Wilkening, H. A.

Melt-Infiltration Process For SiC Ceramics And Composites

Reactive melt infiltration produces silicon carbide-based ceramics and composites faster and more economically than do such processes as chemical vapor infiltration (CVI), reaction sintering, pressureless sintering, hot pressing, and hot isostatic pressing. Process yields dense, strong materials at relatively low cost. Silicon carbide ceramics and composites made by reactive melt infiltration used in combustor liners of jet engines and in nose cones and leading edges of high-speed aircraft and returning spacecraft. In energy industry, materials used in radiant-heater tubes, heat exchangers, heat recuperators, and turbine parts. Materials also well suited to demands of advanced automobile engines.

Behrendt, Donald R.

Reactive Melt Infiltration Of Silicon Into Porous Carbon

Report describes study of synthesis of silicon carbide and related ceramics by reactive melt infiltration of silicon and silicon/molybdenum alloys into porous carbon preforms. Reactive melt infiltration has potential for making components in nearly net shape, performed in less time and at lower temperature. Object of study to determine effect of initial pore volume fraction, pore size, and infiltration material on quality of resultant product.

Behrendt, Donald R.

Theoretical considerations for Reaction-Formed Silicon Carbide (RFSC) formation by molten silicon infiltration into slurry-derived preforms

For reaction-formed silicon carbide (RFSC) ceramics produced by silicon melt infiltration of porous carbon preforms, equations are developed to relate the amount of residual silicon to the initial carbon density. Also, for a slurry derived preform containing both carbon and silicon powder, equations are derived which relate the amount of residual silicon in the RFSC to the relative density of the carbon in the preform and to the amount of silicon powder added to the slurry. For a porous carbon preform that does not have enough porosity to prevent choking-off of the silicon infiltration, these results show that complete silicon infiltration can occur by adding silicon powder to the slurry mixture used to produce these preforms.

Behrendt, D. R.

A study of metal-ceramic wettability in SiC-Al using dynamic melt infiltration of SiC

Pressure-assisted infiltration with a 2014 Al alloy of plain and Cu-coated single crystal platelets of alpha silicon carbide was used to study particulate wettability under dynamic conditions relevant to pressure casting of metal-matrix composites. The total penetration length of infiltrant metal in porous compacts was measured at the conclusion of solidification as a function of pressure, infiltration time, and SiC size for both plain and Cu-coated SiC. The experimental data were analyzed to obtain a threshold pressure for the effect of melt intrusion through SiC compacts. The threshold pressure was taken either directly as a measure of wettability or converted to an effective wetting angle using the Young-Laplace capillary equation. Cu coating resulted in partial but beneficial improvements in wettability as a result of its dissolution in the melt, compared to uncoated SiC.

Asthana, R.