Polymer-derived ceramics (PDCs) which are fabricated through pyrolysis of preceramic polymers have attracted increasing attention due to their versatility in structure architecture design and property tailoring. Shaping at the polymer state using 3D printing allows the final ceramic products to exhibit arbitrary shapes and complex architectures that are otherwise impossible to achieve through traditional processing routes. The polymer-to-ceramic phase transition also provides additional space for mechanical property tailoring. A multiscale computational model is developed to explore the phase transition mechanisms and their correlations with processing parameters and failure response. Calculations in this work concern PMHS/DVB preceramic polymers. Molecular dynamics (MD) simulations are carried out first to track the atomic structure evolution at different temperatures. Continuum-scale ceramic phase formation is calculated on the basis of the competition between gas generation and gas diffusion. The effect of processing parameters on mechanical properties of pyrolyzed PMHS/DVB is systematically studied. Conclusions from this study can provide direct guidance for fabricating PDC composites with tailored mechanical properties.
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Towards Porous Silicon Oxycarbide Materials: Effects of Solvents on Microstructural Features of Poly(methylhydrosiloxane)/Divynilbenzene Aerogels
We investigate the impact of solvents on the microstructure of poly(methylhydrosiloxane)/divinylbenzene (PMHS/DVB) aerogels. The gels are obtained in highly diluted conditions via hydrosilylation reaction of PMHS bearing Si-H groups and cross-linking it with C=C groups of DVB. Polymer aerogels are obtained after solvent exchange with liquid CO2 and subsequent supercritical drying. Samples are characterized using microscopy and porosimetry. Common pore-formation concepts do not provide a solid rationale for the observed data. We postulate that solubility and swelling of the cross-linked polymer in various solvents are major factors governing pore formation of these PMHS/DVB polymer aerogels.
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- NSF-PAR ID:
- 10105087
- Date Published:
- Journal Name:
- Materials
- Volume:
- 11
- Issue:
- 12
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 2589
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Cross‐linking polymethylhydrosiloxane (PMHS) with divinylthiophene (DVT) via hydrosilylation in highly dilute conditions and subsequent supercritical drying in CO2yield a polymeric aerogel containing aromatic sulfur integrally and uniformly distributed throughout the monolith. Fourier‐transform infrared (FT‐IR) spectroscopy indicates almost complete consumption of vinyl groups and SiH bonds in the product. Both FT‐IR and Raman spectroscopic analyses support loss of conjugation of vinyl groups with the retained double bonds of the thiophene ring. Scanning electron microscopy (SEM) indicates a condensed colloidal structure with characteristic particulate diameters of about 165 nm. SEM coupled with energy dispersive X‐ray spectroscopy elemental mapping shows that sulfur is distributed homogeneously in the polymeric aerogel. Porosimetry of the mesoporous aerogel indicates the effective average pore diameters are about 12 nm. Thermogravimetric analysis (TGA) establishes greater thermal stability of the PMHS‐DVT product than either of the pure unreacted components. TGA coupled with mass spectrometric (TG‐MS) identification of the volatiles released during pyrolysis shows that sulfur is driven from the cross‐linked polymer as thiophene and its derivatives. Recorded mass spectra support the hypothesis that cross‐linking DVT bridges between PMHS chains in the polymeric aerogel, and that this results in a more thermally stable monolith.
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Polymer-derived ceramics (PDCs) which are fabricated through pyrolysis of preceramic polymers have attracted increasing attention due to their versatility in structure architecture design and property tailoring. Shaping at the polymer state using 3D printing allows the final ceramic products to exhibit arbitrary shapes and complex architectures that are otherwise impossible to achieve through traditional processing routes. The polymer-to-ceramic phase transition also provides additional space for mechanical property tailoring. A multiscale computational model is developed to explore the phase transition mechanisms and their correlations with processing parameters and mechanical response. Calculations in this work concern PMHS/DVB. Molecular dynamics simulations are carried out first to track the chemical reaction mechanisms and atomic structure evolution. The density of generated gas during pyrolysis is transferred to the finite element model (FEM) for coupled heat transfer and phase transition analysis. FEM calculations reveal the effect of pyrolysis temperature and heating rate on structure-level phase composition and elastic modulus. It is found that there is a threshold of pyrolysis temperature above which full ceramic phase is formed. Higher heating rate promotes ceramization and leads to higher elastic modulus. In addition, volume shrinkage is found to accelerate ceramic formation which slightly enhances material strength.more » « less
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Catalytically active asymmetric membranes were developed by crosslinking a polydimethylsiloxane (PDMS) thin layer onto a porous polyamide‐imide hollow fiber (PAIHF) support, followed by grafting of aminosilane with hydroxyl derived-PDMS/PAIHF, and finally palladium nanoparticles (PdNPs) immobilization using salicylic aldehyde. Aminosilane and salicylic aldehyde linkers were used to permanently immobilize PdNPs onto the PDMS surface through metal coordination chelation, which prevented their agglomeration and leaching from the catalytic membrane reactor (CMR) module. The obtained CMRs were used as a heterogeneous catalyst and continuous-flow membrane reactor for hydrogenation of 4-nitrophenol, aldol and nitroaldol condensation, Heck coupling, CO2 cycloaddition and hydroxyalkylation of aniline, and tandem reactions of glucose and fructose to 5-hydroxymethylfurfural (HMF). Our findings also revealed that the turnover frequency (TOF) and selectivity can be tuned and controlled by adjusting the chemistry and degree of cross-linkers, reaction solvents, and flow rates. Even though our polymeric hollow fiber microreactors showed relatively good performance at temperatures up to 150 °C, some amount of active spices (e.g., Pd nanoparticles) leached out from the microreactor due to polymer swelling, plasticization, and pore shrinkage during flow reaction, especially when exposed to polar aprotic solvents and aromatics, and deteriorated the stability of the immobilized catalysts.more » « less
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Abstract The synthesis of a fluorescent covalent organic framework (COF) using perylene and pyrene building blocks (PEPy‐COF), via a one‐pot condensation reaction is reported. PEPy‐COF is crystallized into 2D nanosheets with a cubic and prismatic crystalline morphology and demonstrates structural stability at temperatures up to 500 °C. The structural morphology is confirmed using X‐ray diffraction and atomic‐level simulations. These 2D porous polymer sheets form a tetragonal framework that is found to have a high specific surface area of 772 m2g−1. Based on the definition of porous materials, the network is mesoporous with an observed pore size of 3.03 nm, which is in good agreement with the material's calculated pore size. The experimentally obtained HOMO‐LUMO band gap is 2.62 eV, confirming the semiconducting nature of PEPy‐COF. PEPy‐COF emits a shiny blue luminescence under UV and visible light. This luminescence intensity is temperature‐dependent in solvents with different polarities and dielectric constants demonstrating that the PEPy‐COF has potential use in a wide range of temperature‐sensing devices. The fluorescence intensity ratio is similar for different temperatures under ultra‐sound conditions and varying solvents.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/ma11122589
