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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Tuning crosslinking of hybrid preceramic polymers in vat photopolymerization toward controlled ceramic yields

Control of preceramic polymer crosslinking for UV-curable processing is essential for fine 3D printing with high ceramic conversion for sustainable polymer-derived ceramics (PDC) engineering. While various factors influencing ceramic yield have been studied, the systematic exploration of the relationship between crosslinking and ceramic yield, especially when crosslinking increases volatile elements, remains open for further investigation. This study addresses this gap by utilizing vat photopolymerization (VP) additive manufacturing (AM) as a versatile platform for controlling preceramic crosslinking and ceramic yield. By rationally designing and tuning the photochemical crosslinking through digital light processing (DLP), we demonstrate that the ceramic yield can be enhanced from 64% to over 86%, even with added volatile elements. We reveal that the post-pyrolysis ceramic yield can be closely correlated with the pre-pyrolysis crosslinking of the preceramic network represented by its stiffness. This correlation thereby suggests a fast, energy-efficient, non-destructive methodology to predict and improve ceramic yield. Combined with these findings, our one-pot thiol-ene hybridization of polycarbosilane and polycarbosiloxane via DLP offers an exemplary method to generate hybrid preceramic polymers with tailored material properties toward target applications, and potentially even higher ceramic yields. This study thus contributes to achieving better resource- and energy-efficient preceramic polymer and PDC processing routes toward sustainable, advanced organic–inorganic materials manufacturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Influence of Thermal Treatment on Preceramic Polymer Grafted Nanoparticle Network Formation: Implications for Thermal Protection Systems and Aerospace Propulsion Components

Preceramic polymer grafted nanoparticles (PCP GNPs) offer potential advantages in the production of polymer-derived ceramic composites compared to neat preceramic polymers (PCPs), such as reduced thermal shrinkage and increased char yield. In comparison to traditional composites (particles + free polymer), PCPs avoid issues of compatibility, agglomeration, and phase separation during processing and provide routes to control nanoparticle arrangement. Prior literature has established that the conversion efficiency of PCPs and PCP GNPs to ceramics and ceramic composites is linked to the thermal pretreatment of these precursor polymers (e.g., curing). In this paper, we investigate the material transformations that occur when exposing PCP GNPs to a low-temperature thermal treatment (≤250 °C) prior to pyrolysis. The PCP GNPs explored in this study possessed silica nanoparticle cores but were distinct in their PCP coronas, having poly(1,1-dimethylpropylsilane) (allyl-GNP)- or poly(1,1-dimethylbenzylethylsilane) (styryl-GNP)-grafted polymers. After undergoing low-temperature thermal treatment, these PCP GNPs exhibited increased char yield at 800 °C; however, unlike commercial PCPs (e.g., allylhydridopolycarbosilane (SMP-10)), obvious cross-linkable sites are not present in the PCP corona structure. Differential scanning calorimetry, oscillatory rheology, and X-ray photon correlation spectroscopy were utilized to elucidate the thermally induced material changes in the allyl- and styryl-GNPs. Thermally induced changes to the structure and behavior of the PCP GNPs were determined to be linked to the chemical structure of the grafted polycarbosilane chains. Styryl-GNPs experienced a curing event between 180 and 250 °C, effecting the formation of a network, which contributed to char yield improvement (at 800 °C). The nanoscale dynamics of this material also shows a transition from diffuse behavior to ballistic behavior because of the cross-linking event. Conversely, the allyl-GNPs did not exhibit a curing event under heat treatment but did show an increase in thermally induced physical cross-linking. The allyl-GNP physical network is stronger after the first cycle of thermal treatment, and it is considered that this contributed to the improvement in char yield post thermal treatment. The advancements in the understanding of the cross-linking behavior of these hybrid materials are expected to advance the application of these materials to turbine engine, advanced friction, and heat-shielding components.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cracking during pyrolysis of preceramic polymers within glass microtubes

Abstract Cracking of preceramic polymers during pyrolysis under highly‐constrained conditions is examined by X‐ray computed tomography of fine glass microtubes containing the pyrolyzing material. The microtubes represent model geometries that mimic the long channels between fibers during production of ceramic composites by precursor impregnation and pyrolysis. Complementary fracture mechanics analyses of interface cracking and crack kinking are used to glean insights into the conditions under which periodic alternating cracks form. A key finding is that alternating cracks are an inherent feature of constrained pyrolysis . This feature is attributable in large part to the high energy release rates for interface cracks to kink into the pyrolyzing material under the hydrostatic tension developed during pyrolysis. It also requires interfaces with toughness comparable to that of the pyrolyzing material, to prevent large‐scale interface separation. The results further indicate the need for small uniform spaces for pyrolysis within fiber preforms in order to produce networks of fine periodic pyrolysis cracks; these networks in turn facilitate impregnation and pyrolysis in subsequent processing cycles.

Larson, Natalie M.↗
DOE OSTI2020

Processing and properties of SiC composites made via binder jet 3D printing and infiltration and pyrolysis of preceramic polymer

The effect of polymer infiltration and pyrolysis (PIP) cycles with polycarbosiloxane on the microstructure, air leak rate, and properties of SiC composites manufactured by a combination of binder jet 3D printing and PIP are reported. The density, Young’s modulus and flexural strength of disk-shaped components increased with the number of PIP cycles. In the case of density, it increased from 2.05 g/cm 3 in one PIP cycle to 2.33 g/cm 3 after three PIP cycles, while values of flexural strength and Young’s modulus at room temperature after three PIP cycles reached 66.8 ± 2.5 MPa and 69.5 ± 2.8 GPa, respectively. Conversely, the air leak rate was found to decrease with number of PIP cycles, and it reached a value of 4 mbar-liter/s after three cycles. The instantaneous coefficient of thermal expansion of the composite was found to change minimally with the number of PIP cycles and had a value of 4 ± 1.2 ppm/°C between 200°C and 1,000°C. Thermal conductivity was found to increase with number of PIP cycles and to decrease with temperature. For example, after 3 PIP cycles it was found to change from 6.72 ± 0.08 to 6.98 ± 0.08 W/mK at 25°C and 7.36 ± 0.08 to 7.96 ± 0.08 W/mK at 300°C. These values were lower than those of crystalline SiC because of the amorphous nature of the matrix and the presence of pores and cracks.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Insights into Preceramic Polymer-Based Additive Manufacturing Inks via Rheological and Scattering Studies of Preceramic Polymer-Grafted Nanoparticles Suspended in Polycarbosilane

Preceramic polymers (PCPs) offer advantages in producing ceramics due to their processability and ability to tailor the final chemistry of the produced material. However, challenges such as volumetric shrinkage and mass loss during pyrolysis often result in polymer-derived ceramics containing pores and cracks. PCP-grafted ceramic nanoparticles (PCPGNPs) have been proposed and studied as a route to mitigate the shrinkage issues associated with neat PCPs. Prior studies on PCPGNPs have principally focused on the synthesis and characterization of neat materials. Dispersing PCPGNPs in commercial preceramic polymer is another attractive, but underexplored, route to control the rheological and char yield properties of PCP systems. In this work, a systematic rheological study of commercial PCP (SMP-877) and PCPGNP (silica with poly(1,1-dimethylpropylsilane) corona) mixtures was executed to develop design rules for the processing of such systems. A rheological study demonstrated the effect of increasing particle concentration on network formation with percolation occurring between 50 and 60 wt %. Samples above the percolation threshold exhibited higher viscosities and rapid shear thinning thus demonstrating their direct-write printability. X-ray photon correlation spectroscopy (XPCS) corroborated the rheology and showed two diffusive modes when the material was above percolation. Mixtures of PCPGNPs and SMP-877 had synergistically higher char yields upon thermal treatment and pyrolysis. XPCS and rheological measurements during thermal treatment identified thermal jamming of the polymer grafts as a key factor in improving the char yield. In conclusion, with the insights gained here, we expect these mixed systems to provide attractive feedstocks for polymer-derived ceramics, with proof-of-principal application as feedstocks for direct ink write (DIW) additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Processing and 3D printing of SiCN polymer-derived ceramics

Preceramic polymer resins are attractive for the 3D printing of net-shaped ceramic components. Recently various processes have been demonstrated for 3D printing of polymer-derived ceramics (PDCs). Ultimately in these processes, the process outcomes strongly depend on the process parameters. In particular, for PDCs the ceramic density, and ceramic yield are affected by the catalyst concentration and cross-linking duration. Here, we use thermal analysis and FTIR to quantify the interrelation of the process parameters on the process outcome for polysilazanes and demonstrate 3D printing of PDC components based on the best-identified process parameters. Furthermore, the results of this work can be used as guidelines for future additive manufacturing of PDCs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reinforcement induced microcracking during the conversion of polymer-derived ceramics

This study investigates the role of discontinuous reinforcement on the microcracking of a preceramic polymer matrix during polymer to ceramic conversion. The material system comprised a carbosilane-based, preceramic polymer reinforced with mullite particles. The preceramic resin slurry was formulated for photopolymerization on a digital light projection 3D printer. Micro X-ray computed tomography, using a synchrotron light source, monitored a printed composite part during pyrolysis. The conversion of the carbosilane matrix into Si(O)C generated microcracks in the matrix that radially extended from particles. The likelihood of microcrack formation positively correlated with particle size. The largest particles (>10 4 µm 3 volume or >60 µm side length) always abutted microcracks, while the matrix surrounding smaller particles (<5 µm) was free of microcracks. Numerical calculations showed the particles resist the shrinking matrix during its conversion. This created tensile stresses within the matrix. The driving force for microcrack growth was also analyzed with regard to the influence of matrix material parameters, particle form-factor and crack length. These results reveal the need to consider the form factor of discontinuous reinforcements, with regard to the material properties of the polymer-derived ceramic, in order to reduce or eliminate defects in the final part.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of Remnant Carbon and Etching of Particles on Pyrolysis Bonded Silicon Carbide (PBSC)

Silicon carbide (SiC) formed through pyrolysis of preceramic polymers loaded with SiC particles has gained significant attention for applications such as coatings, composite matrix modifications, and most importantly additive manufacturing. This work presents combined synchrotron XRD, Raman spectroscopy, scanning electron microscopy, nano-indentation, and Vickers indentation of pyrolysis bonded SiC to shed light on the changes of composition and mechanical properties of these materials. Characterization was performed on samples that were heat treated ranging from the synthesis 850 °C up to 1500 °C. Pre-treatments of the powders prior to pellet synthesis, such as heat treatment and etching using a hydrofluoric acid (HF), were investigated. It is shown that the degradation of mechanical properties when exposed to higher temperatures is due to the burnout of amorphous carbon clusters remnant of the pyrolysis process of the preceramic polymer. Furthermore, prior HF etching and removal of the native oxide layer of the powders showed improved density and hardness values in the final pellets. The average Vickers hardness of the control samples were 4.59 GPa and later 3.74 GPa when exposed to 1500 °C, while the samples synthesized using powders that were etched with HF had an average hardness value of 9.37 GPa and later 6.86 GPa when exposed to 1500 °C.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

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↗
DOE OSTI2026

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↗
DOE OSTI2023

Oxidation performance and limitations of additively manufactured SiC/Si-O-C composites at elevated temperatures

Here, SiC preforms were infiltrated with polycarbosiloxane preceramic polymer to create low-cost SiC—Si x O y C z matrix composites for possible high temperature application. The effect of specimen annealing conditions on the steam and air oxidation resistance was analyzed. Air exposures from 900–1500°C showed stability of the Si x O y C z matrix phase with moderate oxidation resistance. After 900°C exposures, oxidation of the composite is primarily limited to the matrix phase, and only at 1200 and 1500°C was SiC consumption visualized. Steam cycle exposures at 1200°C resulted in rapid linear oxidation of the composites with induced specimen swelling from volume expansion associated with internal oxidation. Specimens annealed in argon were found to be the most oxidation resistant due to increased matrix crystallinity and carbon retention. The results of this work were used to develop clear strategies for improving the high-temperature properties of SiC—Si x O y C z composites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

B‐Staging and Crosslinking of Polycarbosilane at Room Temperature: Cure Mechanism and Properties

The viscosity of polycarbosilane (PCS) polymers is not advantageous for free forming. Various fillers and heat are used to obtain a formable paste. Due to the low yield stress, structures and preforms tend to slump or resin will flow out, especially during the curing of the polymer. B-staging of PCS allows for a more stable structure from room temperature until the full cure of the allyl groups occurs with heat. Additionally, hydrosilation is an effective means of crosslinking at room temperature and controlling viscosity. A network structure was formed in SMP-10 using silane and a vinyl-based crosslinker to bridge each polymer chain. Pt addition catalysts were added to enhance the increase in viscosity to make a lightly crosslinked gel to aid in thickening and forming and to improve the ceramic yield at 1000°C. In conclusion, this enables several options for controlling rheology and improving the properties of preceramic polymers to avoid slumping during curing.

inorganic polymers↗
DOE OSTI2026

A Trifunctional Cyclohexasilane for Branched Poly(cyclosilane)s

The poly(cyclosilane)s are a class of hybrid inorganic-organic polymers with an all Si–Si backbone, arranged into repeating cyclohexasilane motifs, and mixed methyl and hydro side chains. The synthesis of a densely functionalized cyclosilane with three-fold symmetry enabled copolymerization studies yielding poly(cyclosilane)s with variable amounts of branching. The properties of the novel branched poly(cyclosilane)s were investigated and it was found that branching led to less volatilization during pyrolysis in an inert atmosphere, suggesting the utility of poly(cyclosilane)s for applications as preceramic polymers.

Coschigano, Marissa G. [Johns Hopkins University, ↗
DOE OSTI2019

A semi-empirical power-law model for the dip-coating of a substrate into a particle-containing, non-Newtonian, complex fluid system

The apparent viscosity of a particle suspension of ZrSi 2 particles, polyhydromethylsiloxane (PHMS) preceramic polymer and n-Octane solvent, used to process polymer-derived ceramic composite coatings, is shown by viscometric experiments to be shear-thinning. The suspension is dip-coated onto substrates and the measured entrained coating thickness, h 0 , is observed to be a power-law function of U, the substrate extraction speed, as h 0 = 0.5051U 0.5 . The experimentally observed semi-empirical model is directly compared to the results of a variety of theoretically derived Landau-Levich scaling laws and other models that have similar liquids and that include other effects. None of these cases predicts the scaling observed in these experiments. A correction factor is introduced to quantify the difference between the semi-empirical model with existing theoretical models. Possible explanations for the observed scaling behavior are presented.

36 MATERIALS SCIENCE↗
DOE OSTI2018

X-ray computed tomography of microstructure evolution during matrix impregnation and curing in unidirectional fiber beds

Microstructural evolution during axial impregnation and subsequent curing of a preceramic polymer in unidirectional ceramic fiber beds is studied using X-ray computed tomography. The principal goal is to identify connections between void locations, void sizes, local fiber bed porosity, fiber movement, and impregnation conditions. The degree of saturation after impregnation is found to increase with instantaneous capillary number. But, because of the need to create pathways for gas escape during curing, fiber beds with high saturation after impregnation show the largest reductions in saturation during curing. Notwithstanding, saturation after curing increases with instantaneous capillary number. Voids tend to form in the largest channels between fibers, where the local fiber bed porosity is high, during both impregnation and curing. Here, void formation is typically accompanied by fiber movement that increases both the local fiber bed porosity near voids and the overall non-uniformity in the fiber bed, as measured by local porosity entropy.

(A - Material) fibers↗
DOE OSTI2026

Siloxane-modified polycarbosilane flexible Prepregs for fabrication of ceramic matrix composites via compression molding and PIP densification

For this work, the development of ceramic matrix composites (CMCs) using 5 harness satin carbon fiber fabric impregnated with commercial polycarbosilane precursor plasticized by siloxane copolymer was investigated aiming to improve wetting behavior and shape conformability. The polycarbosilane precursor and polysiloxane plasticizer were mixed at varying weight ratios to obtain flexible preceramic resin prepreg cloths. 13 plies of preceramic polymer prepreg cloths were stacked in 0/90° layup and cured by compression molding, followed by densified via PIP process. The CMCs were densified with eight PIP cycles followed by final crystallization at 1600 °C. The CMCs made with 10 wt% polysiloxane loading showed lower viscosity of the prepreg resin as well as higher strength and displacement to failure compared to those fabricated from unplasticized polycarbosilane prepolymer. In contrast, at higher concentration of plasticizer, viscosity of the prepreg resin increased, and the CMC became more brittle; however, it exhibited considerably higher thermal conductivity.

Carbosilane↗
DOE OSTI2020

Tailorable Micelle Morphology in Self-Assembling Block Copolymer Gels for Templating Nanoporous Ceramics

The self-assembly of block copolymers offers opportunities for the facile organization and templating of inorganic nanomaterials. Here, we describe a morphology map for a poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate) (PMMA-b-PnBA-b-PMMA) block copolymer/polycarbosilane system that allows for tunable control over nanoscale micelle geometry via manipulation of the preceramic polymer content. We produced gels with spherical, wormlike, and bicontinuous morphologies, which were processed to create silicon carbide-based ceramic structures with tunable nanoscale porosities. The role of the constituent polymers in influencing the structure and rheology of this system is discussed. The PMMA-b-PnBA-b-PMMA block copolymer/preceramic polymer system offers a number of advantages including: (i) commercial availability, (ii) rapid self-assembly kinetics, and (iii) successful conversion of the self-assembled nanostructure to ceramic via pyrolysis. Finally, this system may be useful for catalytic, structural, or thermal applications in both industrial and academic settings because of its ease of use and relatively inexpensive reagents.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synthesis and Characterization of Silicon Carbide Ceramic Composites with CeO 2 Powder

This study pioneers the fabrication and characterization of silicon carbide (SiC) containing cerium dioxide (CeO 2 ). CeO 2 powder was tested as a surrogate for actinide oxide waste forms such as uranium dioxide (UO 2 ) and plutonium dioxide (PuO 2 ). Several syntheses were evaluated with varying amounts of preceramic polymer (SMP-10 resin) and CeO 2 containing either SiC fiber, carbon fiber, or no fibers. Scanning electron microscopy (SEM) was used to characterize morphology and compositional differences, and energy-dispersive x-ray spectroscopy (EDS) was used to provide semiquantitative elemental analysis. In addition, each sample was characterized by density, powder x-ray diffraction (pXRD), and Raman spectroscopy. Samples containing nearly more than four times CeO 2 powder than SMP-10 resin by mass had the best properties. This research establishes a unique synthesis for SiC containing high concentrations of CeO 2 powder to illustrate how it may be managed as a potential waste form.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗