Browsing by Author "Barnes, Morgan"

Now showing 1 - 6 of 6
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    Direct shape programming of liquid crystal elastomers
    (Royal Society of Chemistry, 2019) Barnes, Morgan; Verduzco, Rafael
    Liquid crystal elastomers (LCEs) are shape morphing materials promising for many applications including soft robotics, actuators, and biomedical devices, but current LCE synthesis techniques lack a simple method to program new and arbitrary shape changes. Here, we demonstrate a straightforward method to directly program complex, reversible, non-planar shape changes in nematic LCEs. We utilize a double network synthesis process that results in a competitive double network LCE. By optimizing the crosslink densities of the first and second network we can mechanically program non-planar shapes with strains between 4–100%. This enables us to directly program LCEs using mechanical deformations that impart low or high strains in the LCE including stamping, curling, stretching and embossing methods. The resulting LCEs reversibly shape-shift between the initial and programmed shape. This work widens the potential application of LCEs in biomedical devices, soft-robotics and micro-fluidics where arbitrary and easily programmed shapes are needed.
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    Enabling Solution Processable COFs through Suppression of Precipitation during Solvothermal Synthesis
    (American Chemical Society, 2022) Khalil, Safiya; Meyer, Matthew D.; Alazmi, Abdullah; Samani, Mohammad H. K.; Huang, Po-Chun; Barnes, Morgan; Marciel, Amanda B.; Verduzco, Rafael; Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment
    Covalent organic frameworks (COFs) are crystalline, nanoporous materials of interest for various applications, but current COF synthetic routes lead to insoluble aggregates which precludes processing for practical implementation. Here, we report a COF synthesis method that produces a stable, homogeneous suspension of crystalline COF nanoparticles that enables the preparation of COF monoliths, membranes, and films using conventional solution-processing techniques. Our approach involves the use of a polar solvent, diacid catalyst, and slow reagent mixing procedure at elevated temperatures which altogether enable access to crystalline COF nanoparticle suspension that does not aggregate or precipitate when kept at elevated temperatures. On cooling, the suspension undergoes a thermoreversible gelation transition to produce crystalline and highly porous COF materials. We further show that the modified synthesis approach is compatible with various COF chemistries, including both large- and small-pore imine COFs, hydrazone-linked COFs, and COFs with rhombic and hexagonal topologies, and in each case, we demonstrate that the final product has excellent crystallinity and porosity. The final materials contain both micro- and macropores, and the total porosity can be tuned through variation of sample annealing. Dynamic light scattering measurements reveal the presence of COF nanoparticles that grow with time at room temperature, transitioning from a homogeneous suspension to a gel. Finally, we prepare imine COF membranes and measure their rejection of polyethylene glycol (PEG) polymers and oligomers, and these measurements exhibit size-dependent rejection and adsorption of PEG solutes. This work demonstrates a versatile processing strategy to create crystalline and porous COF materials using solution-processing techniques and will greatly advance the development of COFs for various applications.
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    Patterning, Transfer, and Tensile Testing of Covalent Organic Framework Films with Nanoscale Thickness
    (American Chemical Society, 2021) Zhu, Dongyang; Hu, Zhiqi; Rogers, Tanya K.; Barnes, Morgan; Tseng, Chia-Ping; Mei, Hao; Sassi, Lucas M.; Zhang, Zhuqing; Rahman, Muhammad M.; Ajayan, Pulickel M.; Verduzco, Rafael
    Covalent organic frameworks (COFs) are promising materials for a variety of applications, including membrane-based separations, thin-film electronics, and as separators for electrochemical devices. Robust mechanical properties are critical to these applications, but there are no reliable methods for patterning COFs or producing free-standing thin films for direct mechanical testing. Mechanical testing of COFs has only been performed on films supported by a rigid substrate. Here, we present a method for patterning, transferring, and measuring the tensile properties of free-floating nanoscale COF films. We synthesized COF powders by condensation of 1,3,5-tris(4-aminophenyl)benzene (TAPB) and terephthalaldehyde (PDA) and prepared uniform thin films by spin casting from a mixture of trifluoroacetic acid and water. The COF films were then reactivated to recover crystallinity and patterned by plasma etching through a poly(dimethylsiloxane) (PDMS) mask. The films were transferred to the surface of water, and we performed direct tensile tests. We measured a modulus of approximately 1.4 GPa for TAPB-PDA COF and a fracture strain of 2.5%, which is promising for many applications. This work advances the development of COFs for thin-film applications by demonstrating a simple and generally applicable approach to cast, pattern, and transfer COF thin films and to perform direct mechanical analysis.
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    Rapid, Ambient Temperature Synthesis of Imine Covalent Organic Frameworks Catalyzed by Transition-Metal Nitrates
    (American Chemical Society, 2021) Zhu, Dongyang; Zhang, Zhuqing; Alemany, Lawrence B.; Li, Yilin; Nnorom, Njideka; Barnes, Morgan; Khalil, Safiya; Rahman, Muhammad M.; Ajayan, Pulickel M.; Verduzco, Rafael
    Covalent organic frameworks (COFs) are crystalline, porous organic materials that are promising for applications including catalysis, energy storage, electronics, gas storage, water treatment, and drug delivery. Conventional solvothermal synthesis approaches require elevated temperatures, inert environments, and long reaction times. Herein, we show that transition-metal nitrates can catalyze the rapid synthesis of imine COFs under ambient conditions. We first tested a series of transition metals for the synthesis of a model COF and found that all transition-metal nitrates tested produced crystalline COF products even in the presence of oxygen. Fe(NO3)3·9H2O was found to produce the most crystalline product, and crystalline COFs could be produced within 10 min by optimizing the catalyst loading. Fe(NO3)3·9H2O was further tested as a catalyst for six different COF targets varying in linker lengths, substituents, and stabilities, and it effectively catalyzed the synthesis of all imine COFs tested. This catalyst was also successful in the synthesis of 2D imine COFs with different geometries, 3D COFs, and azine-linked COFs. This work demonstrates a simple, low-cost approach for the synthesis of imine COFs and will significantly lower the barrier for the development of imine COFs for applications.
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    Transformation of One-Dimensional Linear Polymers into Two-Dimensional Covalent Organic Frameworks Through Sequential Reversible and Irreversible Chemistries
    (American Chemical Society, 2021) Zhu, Dongyang; Li, Xiaoyi; Li, Yilin; Barnes, Morgan; Tseng, Chia-Ping; Khalil, Safiya; Rahman, Muhammad M.; Ajayan, Pulickel M.; Verduzco, Rafael
    Covalent organic frameworks (COFs) are crystalline porous materials linked by dynamic covalent bonds. Dynamic chemistries enable the transformation of an initially amorphous network into a porous and crystalline COF. While dynamic chemistries have been leveraged to realize transformations between different types of COFs, including transformations from two-dimensional (2D) to three-dimensional (3D) COFs and insertion of different linking groups, the transformation of linear polymers into COFs has not yet been reported. Herein, we demonstrate an approach to transform linear imine-linked polymers into ketone-linked COFs through a linker replacement strategy with triformylphloroglucinol (TPG). TPG first reacts through dynamic chemistry to replace linkers in the linear polymers and then undergoes irreversible tautomerism to produce ketone linkages. We have analyzed the time-dependent transformation from the linear polymer into COF through powder X-ray diffraction, Fourier-transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM) to understand the transition and substitution mechanisms. This work demonstrates another route to produce COFs through sequential reversible and irreversible chemistries and provides a potential approach to synthesizing COFs through the solution processing of linear polymers followed by transformation into the desired COF structure.
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    Understanding the effect of liquid crystal content on the phase behavior and mechanical properties of liquid crystal elastomers
    (Royal Society of Chemistry, 2022) Barnes, Morgan; Cetinkaya, Sueda; Ajnsztajn, Alec; Verduzco, Rafael
    Liquid crystal elastomers are stimuli-responsive, shape-shifting materials. They typically require high temperatures for actuation which prohibits their use in many applications, such as biomedical devices. In this work, we demonstrate a simple and general approach to tune the order-to-disorder transition temperature (TODT) or nematic-to-isotropic transition temperature (TNI) of LCEs through variation of the overall liquid crystal mass content. We demonstrate reduction of the TNI in nematic LCEs through the incorporation of non-mesogenic linkers or the addition of lithium salts, and show that the TNI varies linearly with liquid crystal mass content over a broad range, approximately 50 °C. We also analyze data from prior reports that include three different mesogens, different network linking chemistries, and different alignment strategies, and show that the linear trend in TODT with liquid crystal mass content also holds for these systems. Finally, we demonstrate a simple approach to quantifying the maximum actuation strain through measurement of the soft elastic plateau and demonstrate applications of nematic LCEs with low TODTs, including the first body-responsive LCE that curls around a human finger due to body heat, and a fluidic channel that directionally pumps liquid when heated.