Liquid-filled hollow core microstructured polymer optical fiber.

PubMed

Cox, F M; Argyros, A; Large, M C J

2006-05-01

Guidance in a liquid core is possible with microstructured optical fibers, opening up many possibilities for chemical and biochemical fiber-optic sensing. In this work we demonstrate how the bandgaps of a hollow core microstructured polymer optical fiber scale with the refractive index of liquid introduced into the holes of the microstructure. Such a fiber is then filled with an aqueous solution of (-)-fructose, and the resulting optical rotation measured. Hence, we show that hollow core microstructured polymer optical fibers can be used for sensing, whilst also fabricating a chiral optical fiber based on material chirality, which has many applications in its own right.

Unraveling Structure-Property Relationships in Polymer Blends for Intelligent Materials Design

NASA Astrophysics Data System (ADS)

Irwin, Matthew Tyler

Block polymers provide an accessible route to structured, composite materials by combining two or more components with disparate mechanical, chemical, and electrical properties into a single bulk material with nanoscale domains. However, the characteristic lengthscale of these systems is limited, and the choice of components is restricted to those that are able to undergo microstructural ordering at accessible temperatures. This thesis details routes to overcoming these limitations through the addition of a lithium salt, a blend of homopolymers, or both. Chapter 2 describes a study wherein complex sphere phases such as the Frank-Kasper sigma phase can be observed in otherwise disordered asymmetric block polymers through the addition of a lithium salt. Chapter 3 discusses the development and characterization of a ternary polymer blend of an AB diblock copolymer and A and B homopolymers doped with a lithium salt. Detailed characterization showed that doping blends that are otherwise disordered with lithium salt induced microstructural ordering and largely recovers the phase behavior of traditional ternary polymer blends. A systematic study of the ionic conductivity of the blends at a fixed salt concentration demonstrates that, at a given composition, disordered, yet highly structured blends consistently exhibit better conductivity than polycrystalline morphologies with long range order. Chapter 4 extends the methodology of Chapter 3 and details a systematic study of the effects of cross-linker concentration on the performance of polymer electrolyte membranes produced via polymerization-induced microphase separation that exhibit a highly structured, globally disordered microstructure. Finally, Chapter 5 details efforts to develop a water filtration membrane using a polyethylene template derived from a polymeric bicontinuous microemulsion. Throughout all of this work, the goal is to better understand structure-property relationships at the molecular level in order to ultimately inform design criteria for materials where simultaneous control over morphology and mechanical, chemical, or electrical properties is important.

Controlling Microstructure-Transport Interplay in Highly Phase-Separated Perfluorosulfonated Aromatic Multiblock Ionomers via Molecular Architecture Design.

PubMed

Nguyen, Huu-Dat; Assumma, Luca; Judeinstein, Patrick; Mercier, Regis; Porcar, Lionel; Jestin, Jacques; Iojoiu, Cristina; Lyonnard, Sandrine

2017-01-18

Proton-conducting multiblock polysulfones bearing perfluorosulfonic acid side chains were designed to encode nanoscale phase-separation, well-defined hydrophilic/hydrophobic interfaces, and optimized transport properties. Herein, we show that the superacid side chains yield highly ordered morphologies that can be tailored by best compromising ion-exchange capacity and block lengths. The obtained microstructures were extensively characterized by small-angle neutron scattering (SANS) over an extended range of hydration. Peculiar swelling behaviors were evidenced at two different scales and attributed to the dilution of locally flat polymer particles. We evidence the direct correlation between the quality of interfaces, the topology and connectivity of ionic nanodomains, the block superstructure long-range organization, and the transport properties. In particular, we found that the proton conductivity linearly depends on the microscopic expansion of both ionic and block domains. These findings indicate that neat nanoscale phase-separation and block-induced long-range connectivity can be optimized by designing aromatic ionomers with controlled architectures to improve the performances of polymer electrolyte membranes.

Influence of the composite material thermal expansion on embedded highly birefringent polymer microstructured optical fibers

NASA Astrophysics Data System (ADS)

SzelÄ g, M.; Lesiak, P.; Kuczkowski, M.; Domański, A. W.; Woliński, T. R.

2013-05-01

Results of our research on embedded highly birefringent polymer microstructured fibers are presented. A composite material sample with fibers embedded between two layers of a multi-layer composite structure is fabricated and characterized. Temperature sensitivities of the polymer fibers are measured in a free space and compared with the fibers embedded in the composite material. It appeared that highly birefringent polymer microstructured fibers exhibit a strong increase in temperature sensitivity when embedded in the composite material, which is due to the stress-induced changes in birefringence created by thermally-induced strain.

Flow-enhanced solution printing of all-polymer solar cells

DOE PAGES

Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; ...

2015-08-12

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a similar to 90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhancedmore » all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. However, we expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.« less

Flow-enhanced solution printing of all-polymer solar cells

PubMed Central

Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A.; Gu, Kevin; Gu, Xiaodan; Tee, Benjamin C. K.; Pang, Changhyun; Yan, Hongping; Zhao, Dahui; Toney, Michael F.; Mannsfeld, Stefan C. B.; Bao, Zhenan

2015-01-01

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility. PMID:26264528

Lowering the Percolation Threshold of Conductive Composites Using Particulate Polymer Microstructure

NASA Astrophysics Data System (ADS)

Grunlan, Jaime; Gerberich, William; Francis, Lorraine

2000-03-01

In an effort to lower the percolation threshold of carbon black-filled polymer composites, various polymer microstructures were examined. Composites were prepared using polyvinyl acetate (PVAc) latex, PVAc water-dispersible powder and polyvinylpyrrolidone (PVP) solution as the matrix starting material. Composites prepared using the particulate microstructures showed a significantly lowered percolation threshold relative to an equivalently prepared composite using the PVP solution. The PVAc latex-based composites has a percolation threshold of 3 volthe PVP solution-based composite yielded a percolation threshold near 15 voloccupied by polymer particles, the particulate matrix-based composites create a segregated CB network at low filler concentration.

Electrically induced formation of uncapped, hollow polymeric microstructures

NASA Astrophysics Data System (ADS)

Lee, Sung Hun; Kim, Pilnam; Jeong, Hoon Eui; Suh, Kahp Y.

2006-11-01

Uncapped, hollow polymeric microstructures were fabricated on a silicon substrate using electric field induced stretching and detachment. Initially, square or cylinder microposts were generated using a solvent-assisted capillary molding technique, and a featureless electrode mask was positioned on the top of the microstructure with spacers maintaining an air gap (~20 µm). Upon exposure to an external electric field (1.0-3.0 V µm-1), the hollow microstructures were destabilized and stretched by the well-known electrohydrodynamic instability, resulting in contact of the top polymer surface with the mask. Subsequently, detachment of the capping layer occurred upon removal of the mask due to larger adhesion forces at the polymer/mask interface than cohesion forces of the polymer. These hollow microstructures were tested to capture the budding yeast, Saccharomyces cerevisiae, for shear protection.

Photodeposition Method For Fabricating A Three-Dimensional, Patterned Polymer Microstructure

DOEpatents

Walt, David R.; Healey, Brian G.

2001-03-13

The present invention is a photodeposition methodology for fabricating a three-dimensional patterned polymer microstructure. A variety of polymeric structures can be fabricated on solid substrates using unitary fiber optic arrays for light delivery. The methodology allows micrometer-scale photopatterning for the fabricated structures using masks substantially larger than the desired dimensions of the microstructure.

Mechanical Properties of Organized Microcomposites Fabricated by Interference Lithography

NASA Astrophysics Data System (ADS)

Singamaneni, Srikanth; Chang, Sehoon; Jang, Ji-Hyun; Davis, Whitney; Thomas, Edwin; Tsukruk, Vladimir

2009-03-01

We demonstrate that organized, porous, polymer microstructures with continuous open nanoscale pores and sub-micron spacings obtained via interference lithography can be successfully utilized in a highly non-traditional field of ordered microcomposites. Organized microcomposite structures are fabricated by employing two independent strategies, namely, capillary infiltration and in situ polymerization of the rubbery component into the porous glassy microframes. The mechanical properties and ultimate fracture behavior of the single and bicomponent microframes are investigated at different length scales. The ordered single and bi-component microstructures with high degree of control over the microscopic organization of the polymeric phases result in excellent mechanical properties. Combining hard and soft polymer components provides multifunctional materials and coatings with synergetic properties and is frequently utilized for design of advanced polymeric composites.

Diode laser welding of polypropylene: investigations of the microstructures in the welded seam

NASA Astrophysics Data System (ADS)

Abed, S.; Laurens, Patricia; Carretero, C.; Deschamps, J. R.; Duval, C.

2003-03-01

Laser welding of thermoplastic polymers is a non-contact process especially efficient for joining thermoplastic polymers. This innovative technology is already used for industrial series production in different sectors (automobile, packaging,...). The majority of the basic research concerns the weld strength depending on polymer nature, optical properties, butt design and process parameters. Nevertheless, a lack of knowledge concerning the influence of thermal history of the weld seam on morphology of semicrystalline polymer still exists, when this parameter strongly influences the strength of the weld. Actual results of diode laser transmission welding (LTW) experiments on polypropylene, a semicrystalline polymer widely used in industry, could contribute to a better understanding of the process itself and to success in practical applications.

Equilibrium Field Theoretic and Dynamic Mean Field Simulations of Inhomogeneous Polymeric Materials

NASA Astrophysics Data System (ADS)

Chao, Huikuan

Inhomogeneous polymeric materials is a large family of promising materials including but limited to block copolymers (BCPs), polymer nanocomposites (PNCs) and microscopically confined polymer films. The promising application of the materials originates from the materials' unique microstructures, which offer enhanced mechanical, thermal, optical and electrical properties to the materials. Due to the complex interactions and the large parameter space, behaviors of the microstructures formed by grafted nanoparticles and nanorods in PNCs are difficult to understand. Separately, because of relatively weak interactions, the microstructures are typically achieved through rapid processing that are kinetically controlled and beyond equilibrium. However, efficient simulation framework to study nonequilbrium dynamics of the materials is currently not available. To attack the first difficulty, I extended an efficient simulation framework, polymer nanocomposite field theory (PNC-FT), to incorporate grafted nanoparticles and nanorods. This extended framework is demonstrated against existing experimental studies and implemented to study how the nanoparticle design affects the nanoparticle distribution in binary homopolymer blends. The grafted nanoparticle model is also used as a platform to adopt an advanced optimization method to inversely design nanoparticles which are able to self-assemble into targeted two dimensional lattices. The nanorod model under PNC-FT framework is used to investigate the design of nanorod and block copolymer thin films to control the nanorod distribution. To attack the second difficulty, I established an efficient framework (SCMF-LD) based on a recently proposed dynamic mean field theory and used SCMF-LD to study how to kinetically control the nanoparticle distribution at the end of solvent annealing block copolymer thin films. The framework is then extended to incorporate hydrodynamics (SCMF-DPD) and the extended framework is implemented to study morphology development in phase inversion processing polymer thin films, where hydrodynamic effects play an important role. By exploring both equilibrium and nonequilibrium properties in a spectrum of inhomogeneous polymeric material systems, I successfully extended PNC-FT and established SCMF-LD and SCMF-DPD frameworks, which are expected to be efficient and powerful tools in studies of inhomogeneous polymeric material design and processing.

Silicone Polymer Composites for Thermal Protection System: Fiber Reinforcements and Microstructures

DTIC Science & Technology

2010-01-01

angles were tested. Detailed microstructural, mass loss, and peak erosion analyses were conducted on the phenolic -based matrix composite (control) and...silicone-based matrix composites to understand their protective mechanisms. Keywords silicone polymer matrix composites, phenolic polymer matrix...erosion analyses were conducted on the phenolic -based matrix composite (control) and silicone-based matrix composites to understand their protective

Microstructural Characterization of Polymers with Positrons

NASA Technical Reports Server (NTRS)

Singh, Jag J.

1997-01-01

Positrons provide a versatile probe for monitoring microstructural features of molecular solids. In this paper, we report on positron lifetime measurements in two different types of polymers. The first group comprises polyacrylates processed on earth and in space. The second group includes fully-compatible and totally-incompatible Semi-Interpenetrating polymer networks of thermosetting and thermoplastic polyimides. On the basis of lifetime measurements, it is concluded that free volumes are a direct reflection of physical/electromagnetic properties of the host polymers.

Prediction of shock initiation thresholds and ignition probability of polymer-bonded explosives using mesoscale simulations

NASA Astrophysics Data System (ADS)

Kim, Seokpum; Wei, Yaochi; Horie, Yasuyuki; Zhou, Min

2018-05-01

The design of new materials requires establishment of macroscopic measures of material performance as functions of microstructure. Traditionally, this process has been an empirical endeavor. An approach to computationally predict the probabilistic ignition thresholds of polymer-bonded explosives (PBXs) using mesoscale simulations is developed. The simulations explicitly account for microstructure, constituent properties, and interfacial responses and capture processes responsible for the development of hotspots and damage. The specific mechanisms tracked include viscoelasticity, viscoplasticity, fracture, post-fracture contact, frictional heating, and heat conduction. The probabilistic analysis uses sets of statistically similar microstructure samples to directly mimic relevant experiments for quantification of statistical variations of material behavior due to inherent material heterogeneities. The particular thresholds and ignition probabilities predicted are expressed in James type and Walker-Wasley type relations, leading to the establishment of explicit analytical expressions for the ignition probability as function of loading. Specifically, the ignition thresholds corresponding to any given level of ignition probability and ignition probability maps are predicted for PBX 9404 for the loading regime of Up = 200-1200 m/s where Up is the particle speed. The predicted results are in good agreement with available experimental measurements. A parametric study also shows that binder properties can significantly affect the macroscopic ignition behavior of PBXs. The capability to computationally predict the macroscopic engineering material response relations out of material microstructures and basic constituent and interfacial properties lends itself to the design of new materials as well as the analysis of existing materials.

Microfluidic solvent extraction of poly(vinyl alcohol) droplets: effect of polymer structure on particle and capsule formation.

PubMed

Sharratt, W N; Brooker, A; Robles, E S J; Cabral, J T

2018-04-26

We investigate the formation of poly(vinyl alcohol) microparticles by the selective extraction of aqueous polymer solution droplets, templated by microfluidics and subsequently immersed in a non-solvent bath. The role of polymer molecular mass (18-105 kg mol-1), degree of hydrolysis (88-99%) and thus solubility, and initial solution concentration (0.01-10% w/w) are quantified. Monodisperse droplets with radii ranging from 50 to 500 μm were produced at a flow-focusing junction with carrier phase hexadecane and extracted into ethyl acetate. Solvent exchange and extraction result in droplet shrinkage, demixing, coarsening and phase-inversion, yielding polymer microparticles with well-defined dimensions and internal microstructure. Polymer concentration, varied from below the overlap concentration c* to above the concentrated crossover c**, as estimated by viscosity measurements, was found to have the largest impact on the final particle size and extraction timescale, while polymer mass and hydrolysis played a secondary role. These results are consistent with the observation that the average polymer concentration upon solidification greatly exceeds c**, and that the internal microparticle porosity is largely unchanged. However, reducing the initial polymer concentration to well below c* (approximately 100×) and increasing droplet size yields thin-walled (100's of nm) capsules which controllably crumple upon extraction. The symmetry of the process can be readily broken by imposing extraction conditions at an impermeable surface, yielding large, buckled, cavity morphologies. Based on these results, we establish robust design criteria for polymer capsules and particles, demonstrated here for poly(vinyl alcohol), with well-defined shape, dimensions and internal microstructure.

Statistical models and NMR analysis of polymer microstructure

USDA-ARS?s Scientific Manuscript database

Statistical models can be used in conjunction with NMR spectroscopy to study polymer microstructure and polymerization mechanisms. Thus, Bernoullian, Markovian, and enantiomorphic-site models are well known. Many additional models have been formulated over the years for additional situations. Typica...

Active origami by 4D printing

NASA Astrophysics Data System (ADS)

Ge, Qi; Dunn, Conner K.; Qi, H. Jerry; Dunn, Martin L.

2014-09-01

Recent advances in three dimensional (3D) printing technology that allow multiple materials to be printed within each layer enable the creation of materials and components with precisely controlled heterogeneous microstructures. In addition, active materials, such as shape memory polymers, can be printed to create an active microstructure within a solid. These active materials can subsequently be activated in a controlled manner to change the shape or configuration of the solid in response to an environmental stimulus. This has been termed 4D printing, with the 4th dimension being the time-dependent shape change after the printing. In this paper, we advance the 4D printing concept to the design and fabrication of active origami, where a flat sheet automatically folds into a complicated 3D component. Here we print active composites with shape memory polymer fibers precisely printed in an elastomeric matrix and use them as intelligent active hinges to enable origami folding patterns. We develop a theoretical model to provide guidance in selecting design parameters such as fiber dimensions, hinge length, and programming strains and temperature. Using the model, we design and fabricate several active origami components that assemble from flat polymer sheets, including a box, a pyramid, and two origami airplanes. In addition, we directly print a 3D box with active composite hinges and program it to assume a temporary flat shape that subsequently recovers to the 3D box shape on demand.

Fast and cheap fabrication of molding tools for polymer replication

NASA Astrophysics Data System (ADS)

Richter, Christiane; Kirschner, Nadine; Worgull, Matthias; Rapp, Bastian E.

2017-02-01

Polymer replication is a prerequisite for low-cost microstructure components for consumer and end user market. The production of cost-effective microstructure in polymers requires metal molding tools which are often fabricated by direct structuring methods like milling or laser machining both of which are time-consuming and cost-intensive. We present an alternative fabrication method based on replication processes which allows the cheap ( 50 €) and fast ( 12 h) replication of complex microstructures into metal. The process comprises three steps: 1. Generation of the microstructure in a photoresist via lithography. 2. Casting of the structure into a high-temperature silicone which serves as original mold for creation of the metal molding tool. 3. Melting of an eutectic alloy of Sn, Ag and Cu under light pressure directly inside of the silicone within an oven. After cooling to room temperature the metal molding tool can be used for polymer replication into conventional thermoplastic polymers. As a first example we structured polymethylmethacrylate (PMMA) foils with a thickness of 1 mm via hot embossing and feature sizes of 100 μm could be replicated with high fidelity.

Fabrication of nanofibers reinforced polymer microstructures using femtosecond laser material processing

NASA Astrophysics Data System (ADS)

Alubaidy, Mohammed-Amin

A new method has been introduced for the formation of microfeatures made of nanofibers reinforced polymer, using femtosecond laser material processing. The Femtosecond laser is used for the generation of three-dimensional interweaved nanofibers and the construction of microfeatures, like microchannels and voxels, through multi photon polymerization of nanofiber dispersed polymer resin. A new phenomenon of multiphoton polymerization induced by dual wavelength irradiation was reported for the first time. A significant improvement in the spatial resolution, compared to the two photon absorption (2PA) and the three photon absorption (3PA) processes has been achieved. Conductive polymer microstructures and magnetic polymer microstructures have been fabricated through this method. The mechanical properties of nanofiber reinforced polymer microstructures has been investigated by means of nanoindentation and the volume fraction of the generated nanofibers in the nanocomposite was calculated by using nanoindentation analysis. The results showed significant improvement in strength of the material. The electrical conductivity of the two photon polymerization (TPP) generated microfeatures was measured by a two-probe system at room temperature and the conductivity-temperature relationship was measured at a certain temperature range. The results suggest that the conductive polymer microstructure is reproducible and has a consistent conductivity-temperature relation. The magnetic strength has been characterized using Guassmeter. To demonstrate the potential application of the new fabrication method, a novel class of DNA-functionalized three-dimensional (3D), stand-free, and nanostructured electrodes were fabricated. The developed nanofibrous DNA biosensor has been characterized by cyclic voltammetry with the use of ferrocyanide as an electrochemical redox indicator. Results showed that the probe--target recognition has been improved. This research demonstrated that femtosecond laser materials processing is a viable tool of the construction of naomaterial- reinforced polymer microfeatures with tailored properties.

Microstructural Characterization of Polymers by Positron Lifetime Spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Jag J.

1996-01-01

Positrons provide a versatile probe for monitoring microstructural features of molecular solids. In this paper, we report on positron lifetime measurements in two different types of polymers. The first group comprises polyacrylates processed on earth and in space. The second group includes fully-compatible and totally-incompatible Semi-Interpenetrating polymer networks of thermosetting and thermoplastic polyimides. On the basis of lifetime measurements, it is concluded that free volumes are a direct reflection of physical/electromagnetic properties of the host polymers.

Modeling liquid crystal polymeric devices

NASA Astrophysics Data System (ADS)

Gimenez Pinto, Vianney Karina

The main focus of this work is the theoretical and numerical study of materials that combine liquid crystal and polymer. Liquid crystal elastomers are polymeric materials that exhibit both the ordered properties of the liquid crystals and the elastic properties of rubbers. Changing the order of the liquid crystal molecules within the polymer network can induce shape change. These materials are very valuable for applications such as actuators, sensors, artificial muscles, haptic displays, etc. In this work we apply finite element elastodynamics simulations to study the temperature induced shape deformation in nematic elastomers with complex director microstructure. In another topic, we propose a novel numerical method to model the director dynamics and microstructural evolution of three dimensional nematic and cholesteric liquid crystals. Numerical studies presented in this work are in agreement with experimental observations and provide insight into the design of application devices.

Tetrazole amphiphile inducing growth of conducting polymers hierarchical nanostructures and their electromagnetic absorption properties

NASA Astrophysics Data System (ADS)

Xie, Aming; Sun, Mengxiao; Zhang, Kun; Xia, Yilu; Wu, Fan

2018-05-01

Conducting polymers (CPs) at nano scales endow materials with special optical, electrical, and magnetic properties. The crucial factor to construct and regulate the micro-structures of CPs is the inducing reagent, particular in its chemical structure, such active sites, self-assembling properties. In this paper, we design and synthesize an amphiphile bearing tetrazole moiety on its skeleton, and use this amphiphile as an inducing reagent to prepare and regulate the micro-structures of a series of CPs including polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene) and poly(p-phenylenediamine). Because of the unique electric properties of CPs and size effect, we next explored the electromagnetic absorption performances of these CPs nanostructures. A synergetic combination of electric loss and magnetic loss is used to explain the absorption mechanism of these CPs nano-structures.

Directed Self-Assembly in "Breath Figure" Templating of Melamine-Based Amphiphilic Copolymers: Effect of Hydrophilic End-Chain on Honeycomb Film Formation and Wetting.

PubMed

Yin, Hongyao; Feng, Yujun; Billon, Laurent

2018-01-09

Amphiphilic copolymers are widely used in the fabrication of hierarchically honeycomb-structured films through a "breath figure" (BF) process because the hydrophilic block plays a key role in stabilising water templating. However, the hydrophilic monomers reported are mainly confined to acrylic acid and its derivatives, which largely limits understanding of the formation of BF arrays and the introduction of additional functions on porous films. The relationship between polymer composition, film microstructure and surface properties are also less documented. Herein, a novel melamine-based hydrophilic moiety, N-[3-({3-[(4,6-bis{[3-(dimethylamino)propyl]amino}-1,3,5-triazin-2yl)amino]propyl}(methyl)amino)propyl]methacrylamide (ANME), was incorporated into polystyrene (PS) chains by combining atom-transfer radical polymerisation and post-modification to afford three well-defined end-functionalised PS-PANME derivatives. These polymers were used to fabricate honeycomb films through the BF technique. Both inner and outer microstructures of the films were characterised by optical microscopy, AFM and SEM. Polymer hydrophilicity is enhanced upon increasing the PANME content, which results in variation of the film microstructure and porosity, and provokes a transition from Cassie-Baxter to Wenzel behaviour. Furthermore, the surface wettability of as-prepared honeycomb films and corresponding pillared films is mainly governed by film morphology, rather than by the properties of the polymers. Knowledge of the relationships between polymer composition and film structure, as well as surface wettability, is beneficial to design and prepare hierarchically porous films with desirable structures and properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Smart Superwetting Surface with Responsivity in Both Surface Chemistry and Microstructure.

PubMed

Zhang, Dongjie; Cheng, Zhongjun; Kang, Hongjun; Yu, Jianxin; Liu, Yuyan; Jiang, Lei

2018-03-26

Recently, smart surfaces with switchable wettability have aroused much attention. However, only single surface chemistry or the microstructure can be changed on these surfaces, which significantly limits their wetting performances, controllability, and applications. A new surface with both tunable surface microstructure and chemistry was prepared by grafting poly(N-isopropylacrylamide) onto the pillar-structured shape memory polymer on which multiple wetting states from superhydrophilicity to superhydrophobicity can be reversibly and precisely controlled by synergistically regulating the surface microstructure and chemistry. Meanwhile, based on the excellent controllability, we also showed the application of the surface as a rewritable platform, and various gradient wettings can be obtained. This work presents for the first time a surface with controllability in both surface chemistry and microstructure, which starts some new ideas for the design of novel superwetting materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The numerical simulation and experiment on extrusion roller embossing of light diffusion plate with micro-structure

NASA Astrophysics Data System (ADS)

Zang, Gongzheng; Fu, Zhihong; Zhang, Lei; Wan, Yue

2018-01-01

Extrusion roller embossing process has demonstrated the ability to produce polymer film with micro-structure. However the influence of various parameters on the forming quality has not been understood clearly. In this paper, a light diffusion plate with semi cylindrical micro-structure array as the research object, the influence of the main processing parameters such as roller speed, pressuring distance and polymer film temperature to the rolling quality was investigated in detail by simulation and experimental methods. The results show that the thickness of the light diffusion plate and the micro-structure fitting diameter increases with the increasing of the roll speed and the polymer film temperature, and decreases with the increasing of the pressing distance. Besides, the simulation results conformed well to the experimental results.

Manipulating Semicrystalline Polymers in Confinement.

PubMed

Shingne, Nitin; Geuss, Markus; Thurn-Albrecht, Thomas; Schmidt, Hans-Werner; Mijangos, Carmen; Steinhart, Martin; Martín, Jaime

2017-08-17

Because final properties of nanoscale polymeric structures are largely determined by the solid-state microstructure of the confined polymer, it is imperative not only to understand how the microstructure of polymers develops under nanoscale confinement but also to establish means to manipulate it. Here we present a series of processing strategies, adapted from methods used in bulk polymer processing, that allow us to control the solidification of polymer nanostructures. First, we show that supramolecular nucleating agents can be readily used to modify the crystallization kinetics of confined poly(vinylidene fluoride) (PVDF). In addition, we demonstrate that microstructural features that are not traditionally affected by nucleating agents, such as the orientation of crystals, can be tuned with the crystallization temperature applied. Interestingly, we also show that high crystallization temperatures and long annealing periods induce the formation of the γ modification of PVDF, hence enabling the simple production of ferro/piezoelectric nanostructures. We anticipate that the approaches presented here can open up a plethora of new possibilities for the processing of polymer-based nanostructures with tailored properties and functionalities.

Topology Optimization of Lightweight Lattice Structural Composites Inspired by Cuttlefish Bone

NASA Astrophysics Data System (ADS)

Hu, Zhong; Gadipudi, Varun Kumar; Salem, David R.

2018-03-01

Lattice structural composites are of great interest to various industries where lightweight multifunctionality is important, especially aerospace. However, strong coupling among the composition, microstructure, porous topology, and fabrication of such materials impedes conventional trial-and-error experimental development. In this work, a discontinuous carbon fiber reinforced polymer matrix composite was adopted for structural design. A reliable and robust design approach for developing lightweight multifunctional lattice structural composites was proposed, inspired by biomimetics and based on topology optimization. Three-dimensional periodic lattice blocks were initially designed, inspired by the cuttlefish bone microstructure. The topologies of the three-dimensional periodic blocks were further optimized by computer modeling, and the mechanical properties of the topology optimized lightweight lattice structures were characterized by computer modeling. The lattice structures with optimal performance were identified.

Role of Cellulose Nanocrystals on the Microstructure of Maleic Anhydride Plasma Polymer Thin Films.

PubMed

Brioude, Michel M; Roucoules, Vincent; Haidara, Hamidou; Vonna, Laurent; Laborie, Marie-Pierre

2015-07-01

Recently, it was shown that the microstructure of a maleic anhydride plasma polymer (MAPP) could be tailored ab initio by adjusting the plasma process parameters. In this work, we aim to investigate the ability of cellulose nanocrystals (CNCs) to induce topographical structuration. Thus, a new approach was designed based on the deposition of MAPP on CNCs model surfaces. The nanocellulosic surfaces were produced by spin-coating the CNC suspension on a silicon wafer substrate and on a hydrophobic silicon wafer substrate patterned with circular hydrophilic microsized domains (diameter of 86.9 ± 4.9 μm), resulting in different degrees of CNC aggregation. By depositing the MAPP over these surfaces, it was possible to observe that the surface fraction of nanostructures increased from 20% to 35%. This observation suggests that CNCs can act as nucleation points resulting in more structures, although a critical density of the CNCs is required.

Multiscale Modeling of PEEK Using Reactive Molecular Dynamics Modeling and Micromechanics

NASA Technical Reports Server (NTRS)

Pisani, William A.; Radue, Matthew; Chinkanjanarot, Sorayot; Bednarcyk, Brett A.; Pineda, Evan J.; King, Julia A.; Odegard, Gregory M.

2018-01-01

Polyether ether ketone (PEEK) is a high-performance, semi-crystalline thermoplastic that is used in a wide range of engineering applications, including some structural components of aircraft. The design of new PEEK-based materials requires a precise understanding of the multiscale structure and behavior of semi-crystalline PEEK. Molecular Dynamics (MD) modeling can efficiently predict bulk-level properties of single phase polymers, and micromechanics can be used to homogenize those phases based on the overall polymer microstructure. In this study, MD modeling was used to predict the mechanical properties of the amorphous and crystalline phases of PEEK. The hierarchical microstructure of PEEK, which combines the aforementioned phases, was modeled using a multiscale modeling approach facilitated by NASA's MSGMC. The bulk mechanical properties of semi-crystalline PEEK predicted using MD modeling and MSGMC agree well with vendor data, thus validating the multiscale modeling approach.

DNA molecules on periodically microstructured lipid membranes: Localization and coil stretching

NASA Astrophysics Data System (ADS)

Hochrein, Marion B.; Leierseder, Judith A.; Golubović, Leonardo; Rädler, Joachim O.

2007-02-01

We explore large scale conformations of DNA molecules adsorbed on curved surfaces. For that purpose, we investigate the behavior of DNA adsorbed on periodically shaped cationic lipid membranes. These unique membrane morphologies are supported on grooved, one-dimensionally periodic microstructured surfaces. Strikingly, we find that these periodically structured membranes are capable to stretch DNA coils. We elucidate this phenomenon in terms of surface curvature dependent potential energy attained by the adsorbed DNA molecules. Due to it, DNA molecules undergo a localization transition causing them to stretch by binding to highly curved sections (edges) of the supported membranes. This effect provides a new venue for controlling conformations of semiflexible polymers such as DNA by employing their interactions with specially designed biocompatible surfaces. We report the first experimental observation of semiflexible polymers unbinding transition in which DNA molecules unbind from one-dimensional manifolds (edges) while remaining bound to two-dimensional manifolds (cationic membranes).

FAST TRACK COMMUNICATION: Poly(methyl methacrylate)-palladium clusters nanocomposite formation by supersonic cluster beam deposition: a method for microstructured metallization of polymer surfaces

NASA Astrophysics Data System (ADS)

Ravagnan, Luca; Divitini, Giorgio; Rebasti, Sara; Marelli, Mattia; Piseri, Paolo; Milani, Paolo

2009-04-01

Nanocomposite films were fabricated by supersonic cluster beam deposition (SCBD) of palladium clusters on poly(methyl methacrylate) (PMMA) surfaces. The evolution of the electrical conductance with cluster coverage and microscopy analysis show that Pd clusters are implanted in the polymer and form a continuous layer extending for several tens of nanometres beneath the polymer surface. This allows the deposition, using stencil masks, of cluster-assembled Pd microstructures on PMMA showing a remarkably high adhesion compared with metallic films obtained by thermal evaporation. These results suggest that SCBD is a promising tool for the fabrication of metallic microstructures on flexible polymeric substrates.

Rheology and microstructure of filled polymer melts

NASA Astrophysics Data System (ADS)

Anderson, Benjamin John

The states of particle dispersion in polymer nanocomposite melts are studied through rheological characterization of nanocomposite melt mechanical properties and small angle X-ray scattering measurement of the particle microstructure. The particle microstructure probed with scattering is related to bulk flow mechanics to determine the origin of slow dynamics in these complex dispersions: whether a gel or glass transition or a slowing down of dispersing phase dynamics. These studies were conducted to understand polymer mediated particle-particle interactions and potential particle-polymer phase separation. The phase behavior of the dispersion will be governed by enthalpic and entropic contributions. A variety of phases are expected: homogeneous fluid, phase separated, or non-equilibrium gel. The effects of dispersion control parameters, namely particle volume fraction, polymer molecular weight, and polymer-particle surface affinity, on the phase behavior of 44 nm silica dispersions are studied in low molecular weight polyethylene oxide (PEO), polyethylene oxide dimethylether (PEODME), and polytetrahydrofuran (PTHF). Scattering measurements of the particle second virial coefficient in PEO melts indicates repulsive particles by a value slightly greater than unity. In PEO nanocomposites, dispersion dynamics slow down witnessed by a plateau in the elastic modulus as the particle separation approaches the length scale of the polymer radius of gyration. As the polymer molecular weight is increased, the transition shifts to lower particle volume fractions. Below polymer entanglement, the slow dynamics mimics that of a colloidal glass by the appearance of two relaxation times in the viscous modulus that display power law scaling with volume fraction. Above entanglement, the slow dynamics is qualitatively different resembling the behavior of a gelled suspension yet lacking any sign of scattering from particle agglomerates. As polymer molecular weight is increased at a fixed volume fraction, two strain yielding events emerge. Further particle loading leads to the formation of a particle-polymer network and the onset of brittle mechanical behavior. The performance of PEO nanocomposites is contrasted by PEODME and PTHF nanocomposites where a change in the polymer segment-surface activity changes the slow dynamics of the nanocomposite and the microstructure of particles in the melt. Slow dynamics and the particle microstructure indicate a gelled suspension as volume fraction is raised with particles in or near contact and support the turning on of particle attractions in the melt.

Fabrication and characterization of anode-supported micro-tubular solide oxide fuel cell by phase inversion method

NASA Astrophysics Data System (ADS)

Ren, Cong

Nowadays, the micro-tubular solid oxide fuel cells (MT-SOFCs), especially the anode supported MT-SOFCs have been extensively developed to be applied for SOFC stacks designation, which can be potentially used for portable power sources and vehicle power supply. To prepare MT-SOFCs with high electrochemical performance, one of the main strategies is to optimize the microstructure of the anode support. Recently, a novel phase inversion method has been applied to prepare the anode support with a unique asymmetrical microstructure, which can improve the electrochemical performance of the MT-SOFCs. Since several process parameters of the phase inversion method can influence the pore formation mechanism and final microstructure, it is essential and necessary to systematically investigate the relationship between phase inversion process parameters and final microstructure of the anode supports. The objective of this study is aiming at correlating the process parameters and microstructure and further preparing MT-SOFCs with enhanced electrochemical performance. Non-solvent, which is used to trigger the phase separation process, can significantly influence the microstructure of the anode support fabricated by phase inversion method. To investigate the mechanism of non-solvent affecting the microstructure, water and ethanol/water mixture were selected for the NiO-YSZ anode supports fabrication. The presence of ethanol in non-solvent can inhibit the growth of the finger-like pores in the tubes. With the increasing of the ethanol concentration in the non-solvent, a relatively dense layer can be observed both in the outside and inside of the tubes. The mechanism of pores growth and morphology obtained by using non-solvent with high concentration ethanol was explained based on the inter-diffusivity between solvent and non-solvent. Solvent and non-solvent pair with larger Dm value is benefit for the growth of finger-like pores. Three cells with different anode geometries was prepared, La0.85Sr0.15MnO 3 (LSM) was selected as the cathode. Cells were tested at 800°C using humidified H2 as fuel. Cell with anode prepared by using pure water as non-solvent shows a maximum power density up to 437mW/cm 2. By comparing the anode geometry and electrochemical performance, it indicated that microstructure with longer finger-like pores and thinner macrovoid free layer close to the inner side of the tube is benefit to cell performance. Another factor that can affect the microstructure of anode support is the ratio of solvent and polymer binder. In this research, anode-supported MT-SOFCs have been fabricated by phase inversion method. The effect of the viscosity of the casting slurry on the microstructure of YSZ-NiO anode support has been investigated. The microstructure of the YSZ-NiO support can be effectively controlled by varying the slurry composition with different solvent and polymer binder content. Gas permeation and mechanical strength of the YSZ-NiO support have been measured and four YSZ-NiO anode supports have been chosen for subsequent cell fabrication. The effective conductivity of the different anode supports has been measured at room temperature after reduced. Anode-supported single cells with YSZ electrolyte and LSM/YSZ cathode are fabricated and tested. Maximum cell power densities of 606 mWcm-2, 449 mWcm -2, 339 mWcm-2 and 253 mWcm-2 have been obtained respectively at 750 °C with humidified hydrogen as fuel and ambient air as oxidant. The correlation between the cell electrochemical performance and anode microstructures has been discussed. Adjusting the slurry composition by introducing additive is also an effective approach to tailor the microstructure of the anode support. Poly(ethylene glycol) (PEG), which is a common applied polymer additive, was selected to fabricate the YSZ-NiO anode supports. The effect of molecular weight and amount of PEG additive on the thermodynamics of the casting solutions was characterized by measuring the coagulation value. Viscosity of the casting slurries was also measured and the influence of PEG additive on viscosity was studied and discussed. The presence of PEG in the casting slurry can greatly influence the final anode support microstructure. Based on the microstructure result and the measured gas permeation value, two anode supports were selected for cell fabrication. For cell with the anode support fabricated using slurry with PEG additive, a maximum cell power density of 704 mWcm-2 is obtained at 750 oC with humidified hydrogen as fuel and ambient air as oxidant; cell fabricated without any PEG additive shows the peak cell power density of 331 mWcm-2. The relationship between anode microstructure and cell performance was discussed. Anode-supported micro-tubular solid oxide fuel cells (MT-SOFCs) based on BaZr0.1Ce0.7Y0.1Yb0.1O 3-delta (BZCYYb) proton-conducting electrolyte have been prepared using a phase inversion method. Three sulfur-free polymer binder candidates ethyl cellulose (EC), polyvinylidene fluoride (PVDF), polyetherimide (PEI) and sulfur-containing polythersulfone (PESf) were used as polymer binders to fabricate NiO-BZCYYb anode. The overall influence of polymer binder on the anode supports was evaluated. Sulfide impurity generated from PESf was revealed by XRD and X-ray photoelectron spectroscopy (XPS). The difference in the anode microstructure for samples fabricated by different polymer binders was examined by scanning electron microscope (SEM) and analyzed by measuring the gas permeation data of the reduced samples. Single cells based on different anode supports were characterized in anode-supported MT-SOFCs with the cell configuration of Ni-BZCYYb anode, BZCYYb electrolyte and La0.6Sr 0.4Co0.2Fe0.8O3-delta (LSCF)-BZCYYb cathode at 650 °C using hydrogen as fuel and ambient air as oxidant. MT-SOFCs of the anode fabricated using PEI show maximum power density of 0.45 Wcm -2 compared with 0.35 Wcm-2 for cells fabricated with PESf. The difference in cell performance was attributed to the phase purity of the anode fabricated by different polymer binders. Sulfur-free polymer binder PEI exhibits advantages over the commonly applied PESf and other sulfur-free polymer binder candidates. To eliminate the skin layer formed close to the inner side of the tubular sample when using the phase inversion method. Polyethersulfone (PESf)-polyethylenimine (PEI) blend was employed as the polymer binder to fabricate the micro-tubular solid oxide fuel cells (MT-SOFCs). The potential impurity introduced in the anode support by the polymer binder was examined by XPS and the resulting novel microstructure was analyzed based on the backscattered electron (BSE) images. Cells fabricated with blend polymer binder showed significantly enhanced power output compared with those cells only fabricated with PEI or PESf. The improved cell performance demonstrated that using blend polymer as binder is a promising and versatile approach for MT-SOFC fabrication via phase inversion method. Finally, to investigate the effect of the anode microstructure on the total cell performance, two types of anode support with different microstructure were prepared via the phase inversion method at different temperature. Cells fabricated based on these two anode supports were tested at 750 °C with hydrogen or hydrogen mixture with fuel gas. The measured current density-voltage (I-V) curves were fitted by a polarization model, and several parameters were archived through the modeling process. The influence of the anode support on the total cell performance was discussed based on the calculated result.

Biocompatible, Biodegradable Polymers for Use in Bone Repair,

DTIC Science & Technology

1987-01-01

as intact polymers and because their degradation products are carbon dioxide and water. 7 B. Microstructure, Morphology, Synthesis The microstructure...Hydrophilic flIe x iblIe 0 6. Carbonate R-O-C-O-R Hydrophilic r ig id Hollinger Ibav %lark page 15 D. Potential Biodegradable Polymers For producing high...diacids or hydroxvacids. Lactone rings with three to six carbons within the ring can be used as monomers. This limits the ratio ot sp4 to sp2 carbons

Hydrothermal Growth of ZnO Nanowires on UV-Nanoimprinted Polymer Structures.

PubMed

Park, Sooyeon; Moore, Sean A; Lee, Jaejong; Song, In-Hyouk; Farshchian, Bahador; Kim, Namwon

2018-05-01

Integration of zinc oxide (ZnO) nanowires on miniaturized polymer structures can broaden its application in multi-functional polymer devices by taking advantages of unique physical properties of ZnO nanowires and recent development of polymer microstructures in analytical systems. In this paper, we demonstrate the hydrothermal growth of ZnO nanowires on polymer microstructures fabricated by UV nanoimprinting lithography (NIL) using a polyurethane acrylate (PUA). Since PUA is a siloxane-urethane-acrylate compound containing the alpha-hydroxyl ketone, UV-cured PUA include carboxyl groups, which inhibit and suppress the nucleation and growth of ZnO nanowires on polymer structures. The presence of carboxyl groups in UV-cured PUA was substantiated by Fourier transform infrared spectroscopy (FTIR), and a Ag thin film was deposited on the nanoimprinted polymer structures to limit their inhibitive influence on the growth of ZnO nanowires. Furthermore, the naturally oxidized Ag layer (Ag2O) reduced crystalline lattice mismatches at the interface between ZnO-Ag during the seed annealing process. The ZnO nanowires grown on the Ag-deposited PUA microstructures were found to have comparable morphological characteristics with ZnO nanowires grown on a Si wafer.

Formation of Foam-like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand-Assisted Foaming Process.

PubMed

Kongpatpanich, Kanokwan; Horike, Satoshi; Fujiwara, Yu-Ichi; Ogiwara, Naoki; Nishihara, Hirotomo; Kitagawa, Susumu

2015-09-14

Porous carbon material with a foam-like microstructure has been synthesized by direct carbonization of porous coordination polymer (PCP). In situ generation of foaming agents by chemical reactions of ligands in PCP during carbonization provides a simple way to create lightweight carbon material with a foam-like microstructure. Among several substituents investigated, the nitro group has been shown to be the key to obtain the unique foam-like microstructure, which is due to the fast kinetics of gas evolution during carbonization. Foam-like microstructural carbon materials showed higher pore volume and specific capacitance compared to a microporous carbon. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of porous asphalt microstructure using optical and electron microscopy.

PubMed

Poulikakos, L D; Partl, M N

2010-11-01

Direct observations of porous asphalt concrete samples in their natural state using optical and electron microscopy techniques led to useful information regarding the microstructure of two mixes and indicated a relationship between microstructure and in situ performance. This paper presents evidence that suboptimal microstructure can lead to premature failure thus making a first step in defining well or suboptimal performing pavements with a bottom-up approach (microstructure). Laboratory and field compaction produce different samples in terms of the microstructure. Laboratory compaction using the gyratory method has produced more microcracks in mineral aggregates after the binder had cooled. Well-performing mixes used polymer-modified binders, had a more homogeneous void structure with fewer elongated voids and better interlocking of the aggregates. Furthermore, well-performing mixes showed better distribution of the mastic and better coverage of the aggregates with bitumen. Low vacuum scanning electron microscopy showed that styrene butadiene styrene polymer modification in binder exists in the form of discontinuous globules and not continuous networks. A reduction in the polymer phase was observed as a result of aging and in-service use. © 2010 The Authors Journal compilation © 2010 The Royal Microscopical Society.

Microstructured Polymer Blend Surfaces Produced by Spraying Functional Copolymers and Their Blends

PubMed Central

Vargas-Alfredo, Nelson; Rodríguez Hernández, Juan

2016-01-01

We described the fabrication of functional and microstructured surfaces from polymer blends by spray deposition. This simple technique offers the possibility to simultaneously finely tune the microstructure as well as the surface chemical composition. Whereas at lower polymer concentration, randomly distributed surface micropatterns were observed, an increase of the concentration leads to significant changes on these structures. On the one hand, using pure homopolystyrene fiber-like structures were observed when the polymer concentration exceeded 30 mg/mL. Interestingly, the incorporation of 2,3,4,5,6-pentafluorostyrene changed the morphology, and, instead of fibers, micrometer size particles were identified at the surface. These fluorinated microparticles provide superhydrophobic properties leading to surfaces with contact angles above 165°. Equally, in addition to the microstructures provided by the spray deposition, the use of thermoresponsive polymers to fabricate interfaces with responsive properties is also described. Contact angle measurements revealed variations on the surface wettability upon heating when blends of polystyrene and polystyrene-b-poly(dimethylaminoethyl methacrylate) are employed. Finally, the use of spraying techniques to fabricate gradient surfaces is proposed. Maintaining a constant orientation, the surface topography and thus the contact angle varies gradually from the center to the edge of the film depending on the spray angle. PMID:28773555

Structural Polymer-Based Carbon Nanotube Composite Fibers: Understanding the Processing–Structure–Performance Relationship

PubMed Central

Song, Kenan; Zhang, Yiying; Meng, Jiangsha; Green, Emily C.; Tajaddod, Navid; Li, Heng; Minus, Marilyn L.

2013-01-01

Among the many potential applications of carbon nanotubes (CNT), its usage to strengthen polymers has been paid considerable attention due to the exceptional stiffness, excellent strength, and the low density of CNT. This has provided numerous opportunities for the invention of new material systems for applications requiring high strength and high modulus. Precise control over processing factors, including preserving intact CNT structure, uniform dispersion of CNT within the polymer matrix, effective filler–matrix interfacial interactions, and alignment/orientation of polymer chains/CNT, contribute to the composite fibers’ superior properties. For this reason, fabrication methods play an important role in determining the composite fibers’ microstructure and ultimate mechanical behavior. The current state-of-the-art polymer/CNT high-performance composite fibers, especially in regards to processing–structure–performance, are reviewed in this contribution. Future needs for material by design approaches for processing these nano-composite systems are also discussed. PMID:28809290

Friction behavior of a microstructured polymer surface inspired by snake skin.

PubMed

Baum, Martina J; Heepe, Lars; Gorb, Stanislav N

2014-01-01

The aim of this study was to understand the influence of microstructures found on ventral scales of the biological model, Lampropeltis getula californiae, the California King Snake, on the friction behavior. For this purpose, we compared snake-inspired anisotropic microstructured surfaces to other microstructured surfaces with isotropic and anisotropic geometry. To exclude that the friction measurements were influenced by physico-chemical variations, all friction measurements were performed on the same epoxy polymer. For frictional measurements a microtribometer was used. Original data were processed by fast Fourier transformation (FFT) with a zero frequency related to the average friction and other peaks resulting from periodic stick-slip behavior. The data showed that the specific ventral surface ornamentation of snakes does not only reduce the frictional coefficient and generate anisotropic frictional properties, but also reduces stick-slip vibrations during sliding, which might be an adaptation to reduce wear. Based on this extensive comparative study of different microstructured polymer samples, it was experimentally demonstrated that the friction-induced stick-slip behavior does not solely depend on the frictional coefficient of the contact pair.

Computational Prediction of Shock Ignition Thresholds and Ignition Probability of Polymer-Bonded Explosives

NASA Astrophysics Data System (ADS)

Wei, Yaochi; Kim, Seokpum; Horie, Yasuyuki; Zhou, Min

2017-06-01

A computational approach is developed to predict the probabilistic ignition thresholds of polymer-bonded explosives (PBXs). The simulations explicitly account for microstructure, constituent properties, and interfacial responses and capture processes responsible for the development of hotspots and damage. The specific damage mechanisms considered include viscoelasticity, viscoplasticity, fracture, post-fracture contact, frictional heating, and heat conduction. The probabilistic analysis uses sets of statistically similar microstructure samples to mimic relevant experiments for statistical variations of material behavior due to inherent material heterogeneities. The ignition thresholds and corresponding ignition probability maps are predicted for PBX 9404 and PBX 9501 for the impact loading regime of Up = 200 --1200 m/s. James and Walker-Wasley relations are utilized to establish explicit analytical expressions for the ignition probability as a function of load intensities. The predicted results are in good agreement with available experimental measurements. The capability to computationally predict the macroscopic response out of material microstructures and basic constituent properties lends itself to the design of new materials and the analysis of existing materials. The authors gratefully acknowledge the support from Air Force Office of Scientific Research (AFOSR) and the Defense Threat Reduction Agency (DTRA).

Structural characterization of semicrystalline polymer morphologies by imaging-SANS

NASA Astrophysics Data System (ADS)

Radulescu, A.; Fetters, L. J.; Richter, D.

2012-02-01

Control and optimization of polymer properties require the global knowledge of the constitutive microstructures of polymer morphologies in various conditions. The microstructural features can be typically explored over a wide length scale by combining pinhole-, focusing- and ultra-small-angle neutron scattering (SANS) techniques. Though it proved to be a successful approach, this involves major efforts related to the use of various scattering instruments and large amount of samples and the need to ensure the same crystallization kinetics for the samples investigated at various facilities, in different sample cell geometries and at different time intervals. With the installation and commissioning of the MgF2 neutron lenses at the KWS-2 SANS diffractometer installed at the Heinz Maier-Leibnitz neutron source (FRMII reactor) in Garching, a wide Q-range, between 10-4Å-1 and 0.5Å-1, can be covered at a single instrument. This enables investigation of polymer microstructures over a length scale from lnm up to 1μm, while the overall polymer morphology can be further examined up to 100μm by optical microscopy (including crossed polarizers). The study of different semi-crystalline polypropylene-based polymers in solution is discussed and the new imaging-SANS approach allowing for an unambiguous and complete structural characterization of polymer morphologies is presented.

Molecularly designed lipid microdomains for solid dispersions using a polymer/inorganic carrier matrix produced by hot-melt extrusion.

PubMed

Adler, Camille; Schönenberger, Monica; Teleki, Alexandra; Kuentz, Martin

2016-02-29

Amorphous solid dispersions have for many years been a focus in oral formulations, especially in combination with a hot-melt extrusion process. The present work targets a novel approach with a system based on a fatty acid, a polymer and an inorganic carrier. It was intended to adsorb the acidic lipid by specific molecular interactions onto the solid carrier to design disorder in the alkyl chains of the lipid. Such designed lipid microdomains (DLM) were created as a new microstructure to accommodate a compound in a solid dispersion. Vibrational spectroscopy, X-ray powder diffraction, atomic force microscopy as well as electron microscopic imaging were employed to study a system of stearic acid, hydroxypropylcellulose and aluminum magnesium silicate. β-carotene was used as a poorly water-soluble model substance that is difficult to formulate with conventional solid dispersion formulations. The results indicated that the targeted molecular excipient interactions indeed led to DLMs for specific compositions. The different methods provided complementary aspects and important insights into the created microstructure. The novel delivery system appeared to be especially promising for the formulation of oral compounds that exhibit both high crystal energy and lipophilicity. Copyright © 2015 Elsevier B.V. All rights reserved.

Microstructure of Pharmaceutical Semicrystalline Dispersions: The Significance of Polymer Conformation.

PubMed

Van Duong, Tu; Goderis, Bart; Van Humbeeck, Jan; Van den Mooter, Guy

2018-02-05

The microstructure of pharmaceutical semicrystalline solid dispersions has attracted extensive attention due to its complexity that might result in the diversity in physical stability, dissolution behavior, and pharmaceutical performance of the systems. Numerous factors have been reported that dictate the microstructure of semicrystalline dispersions. Nevertheless, the importance of the complicated conformation of the polymer has never been elucidated. In this study, we investigate the microstructure of dispersions of polyethylene glycol and active pharmaceutical ingredients by small-angle X-ray scattering and high performance differential scanning calorimetry. Polyethylene glycol with molecular weight of 2000 g/mol (PEG2000) and 6000 g/mol (PEG6000) exhibited remarkable discrepancy in the lamellar periodicity in dispersions with APIs which was attributed to the differences in their folding behavior. The long period of PEG2000 always decreased upon aging-induced exclusion of APIs from the interlamellar region of extended chain crystals whereas the periodicity of PEG6000 may decrease or increase during storage as a consequence of the competition between the drug segregation and the lamellar thickening from nonintegral-folded into integral-folded chain crystals. These processes were in turn significantly influenced by the crystallization tendency of the pharmaceutical compounds, drug-polymer interactions, as well as the dispersion composition and crystallization temperature. This study highlights the significance of the polymer conformation on the microstructure of semicrystalline systems that is critical for the preparation of solid dispersions with consistent and reproducible quality.

Magnetically assisted slip casting of bioinspired heterogeneous composites

NASA Astrophysics Data System (ADS)

Le Ferrand, Hortense; Bouville, Florian; Niebel, Tobias P.; Studart, André R.

2015-11-01

Natural composites are often heterogeneous to fulfil functional demands. Manufacturing analogous materials remains difficult, however, owing to the lack of adequate and easily accessible processing tools. Here, we report an additive manufacturing platform able to fabricate complex-shaped parts exhibiting bioinspired heterogeneous microstructures with locally tunable texture, composition and properties, as well as unprecedentedly high volume fractions of inorganic phase (up to 100%). The technology combines an aqueous-based slip-casting process with magnetically directed particle assembly to create programmed microstructural designs using anisotropic stiff platelets in a ceramic, metal or polymer functional matrix. Using quantitative tools to control the casting kinetics and the temporal pattern of the applied magnetic fields, we demonstrate that this approach is robust and can be exploited to design and fabricate heterogeneous composites with thus far inaccessible microstructures. Proof-of-concept examples include bulk composites with periodic patterns of microreinforcement orientation, and tooth-like bilayer parts with intricate shapes exhibiting site-specific composition and texture.

Microstructural Parameters in 8 MeV Electron-Irradiated BOMBYX MORI Silk Fibers by Wide-ANGLE X-Ray Scattering Studies (waxs)

NASA Astrophysics Data System (ADS)

Sangappa, Asha, S.; Sanjeev, Ganesh; Subramanya, G.; Parameswara, P.; Somashekar, R.

2010-01-01

The present work looks into the microstructural modification in electron irradiated Bombyx mori P31 silk fibers. The irradiation process was performed in air at room temperature using 8 MeV electron accelerator at different doses: 0, 25, 50 and 100 kGy. Irradiation of polymer is used to cross-link or degrade the desired component or to fix the polymer morphology. The changes in microstructural parameters in these natural polymer fibers have been computed using wide angle X-ray scattering (WAXS) data and employing line profile analysis (LPA) using Fourier transform technique of Warren. Exponential, Lognormal and Reinhold functions for the column length distributions have been used for the determination of crystal size, lattice strain and enthalpy parameters.

Highly birefringent polymer microstructured optical fibers embedded in composite materials

NASA Astrophysics Data System (ADS)

Lesiak, P.; SzelÄ g, M.; Kuczkowski, M.; Domański, A. W.; Woliński, T. R.

2013-05-01

Composite structures are made from two or more constituent materials with significantly different physical or chemical properties and they remain separate and distinct in a macroscopic level within the finished structure. This feature allows for introducing highly birefringent polymer microstructured optical fibers into the composite material. These new fibers can consist of only two polymer materials (PMMA and PC) with similar value of the Young modulus as the composite material so any stresses induced in the composite material can be easily measured by the proposed embedded fiber optic sensors.

Microfluidic devices with permeable polymer barriers for capture and transport of biomolecules and cells.

PubMed

Lee, Ho Suk; Chu, Wai Keung; Zhang, Kun; Huang, Xiaohua

2013-09-07

We report a method for fabricating permeable polymer microstructure barriers in polydimethylsiloxane (PDMS) microfluidic devices and the use of the devices to capture and transport DNA and cells. The polymer microstructure in a desired location in a fluidic channel is formed in situ by the polymerization of acrylamide and polyethylene diacrylate cross-linker (PEG-DA) monomer in a solution which is trapped in the location using a pair of PDMS valves. The porous polymer microstructure provides a mechanical barrier to convective fluid flow in the channel or between two microfluidic chambers while it still conducts ions or small charged species under an electric field, allowing for the rapid capture and transport of biomolecules and cells by electrophoresis. We have demonstrated the application of the devices for the rapid capture and efficient release of bacteriophage λ genomic DNA, solution exchange and for the transport and capture of HeLa cells. Our devices will enable the multi-step processing of biomolecules and cells or individual cells within a single microfluidic chamber.

Realising damage-tolerant nacre-inspired CFRP

NASA Astrophysics Data System (ADS)

Narducci, F.; Lee, K.-Y.; Pinho, S. T.

2018-07-01

In this work, a nacre-inspired Carbon Fibre Reinforced Polymer (CFRP) composite is designed, synthesised and tested. Analytical and numerical models are used to design a tiled micro-structure, mimicking the staggered arrangement of ceramic platelets in nacre and exploiting geometrical interlocks for crack deflection and damage diffusion. The designed pattern of tiles is then laser-engraved in the laminate plies. In order to increase the damage-spreading capability of the material, a thin layer of poly(lactic acid) (PLA) is film-cast on the interlaminar region, both as a continuous film and as a pattern of fractal-shaped patches. Three-point bending tests show how the nacre-like micro-structure succeeds in deflecting cracks, with damage diffusion being significantly improved by the addition of PLA at the interface between tiles. It is observed that a texture of discontinuous fractal-shaped PLA patches can increase damage diffusion, by promoting the unlocking of tiles whilst preserving the interface strength.

Investigations on the Mechanical Properties of Conducting Polymer Coating-Substrate Structures and Their Influencing Factors

PubMed Central

Wang, Xi-Shu; Tang, Hua-Ping; Li, Xu-Dong; Hua, Xin

2009-01-01

This review covers recent advances and work on the microstructure features, mechanical properties and cracking processes of conducting polymer film/coating- substrate structures under different testing conditions. An attempt is made to characterize and quantify the relationships between mechanical properties and microstructure features. In addition, the film cracking mechanism on the micro scale and some influencing factors that play a significant role in the service of the film-substrate structure are presented. These investigations cover the conducting polymer film/coating nucleation process, microstructure-fracture characterization, translation of brittle-ductile fractures, and cracking processes near the largest inherent macromolecule defects under thermal-mechanical loadings, and were carried out using in situ scanning electron microscopy (SEM) observations, as a novel method for evaluation of interface strength and critical failure stress. PMID:20054470

The effect of confinement on the crystalline microstructure of polymer: fullerene bulk heterojunctions

DOE PAGES

Ashraf, A.; Dissanayake, D. M. N. M.; Eisaman, M. D.

2015-07-01

We investigate the effect of confinement on the coherence length and the crystalline microstructure of the polymer component of polymer: fullerene bulk heterojunction thin films using grazing incidence wide angle x-ray scattering. We find that the polymer crystallite size decreases and the alignment of the molecules along the surface normal increases, as the thin-film thickness is reduced from 920nm to < 20nm and approaches the thin-film confinement regime. Furthermore, we find that the polymer crystallite size near the surface (air interface) is lower than the crystallite size in the bulk or the bottom (substrate interface) of bulk heterojunction films thickermore » than the confinement regime. Variation in polymer crystallite size can cause changes in charge carrier mobility and recombination rates, which in turn affect the performance of bulk heterojunction thin film devices such as photovoltaics and photodetectors« less

Modeling Percolation in Polymer Nanocomposites by Stochastic Microstructuring

PubMed Central

Soto, Matias; Esteva, Milton; Martínez-Romero, Oscar; Baez, Jesús; Elías-Zúñiga, Alex

2015-01-01

A methodology was developed for the prediction of the electrical properties of carbon nanotube-polymer nanocomposites via Monte Carlo computational simulations. A two-dimensional microstructure that takes into account waviness, fiber length and diameter distributions is used as a representative volume element. Fiber interactions in the microstructure are identified and then modeled as an equivalent electrical circuit, assuming one-third metallic and two-thirds semiconductor nanotubes. Tunneling paths in the microstructure are also modeled as electrical resistors, and crossing fibers are accounted for by assuming a contact resistance associated with them. The equivalent resistor network is then converted into a set of linear equations using nodal voltage analysis, which is then solved by means of the Gauss–Jordan elimination method. Nodal voltages are obtained for the microstructure, from which the percolation probability, equivalent resistance and conductivity are calculated. Percolation probability curves and electrical conductivity values are compared to those found in the literature. PMID:28793594

Micro-Nanostructures of Cellulose-Collagen for Critical Sized Bone Defect Healing.

PubMed

Aravamudhan, Aja; Ramos, Daisy M; Nip, Jonathan; Kalajzic, Ivo; Kumbar, Sangamesh G

2018-02-01

Bone tissue engineering strategies utilize biodegradable polymeric matrices alone or in combination with cells and factors to provide mechanical support to bone, while promoting cell proliferation, differentiation, and tissue ingrowth. The performance of mechanically competent, micro-nanostructured polymeric matrices, in combination with bone marrow stromal cells (BMSCs), is evaluated in a critical sized bone defect. Cellulose acetate (CA) is used to fabricate a porous microstructured matrix. Type I collagen is then allowed to self-assemble on these microstructures to create a natural polymer-based, micro-nanostructured matrix (CAc). Poly (lactic-co-glycolic acid) matrices with identical microstructures serve as controls. Significantly higher number of implanted host cells are distributed in the natural polymer based micro-nanostructures with greater bone density and more uniform cell distribution. Additionally, a twofold increase in collagen content is observed with natural polymer based scaffolds. This study establishes the benefits of natural polymer derived micro-nanostructures in combination with donor derived BMSCs to repair and regenerate critical sized bone defects. Natural polymer based materials with mechanically competent micro-nanostructures may serve as an alternative material platform for bone regeneration. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Smart assembly of polymer fibers: lessons from major ampullate spider silk

NASA Astrophysics Data System (ADS)

Viney, Christopher

1996-02-01

Studies of major ampullate silk (MAS), especially the secretions and fibers produced by the spider Nephila clavipes (golden orb weaver), have yielded several results of potential value to the materials scientist/engineer. There are lessons to be learned about synthesis, processing and microstructural design of high-tensile polymer fibers. The 'smart' aspect of silk production in nature concerns the ability of the spider to rapidly process a concentrated, viscous aqueous solution of silk protein (stored in the gland) into water-insoluble fiber on demand. This process centers on the assembly of a shear-sensitive supramolecular liquid crystalline phase by aggregation of the solubilized globular protein molecules.

Characterization of a polymer-infiltrated ceramic-network material

PubMed Central

Corazza, Pedro H.; Zhang, Yu

2015-01-01

Objectives To characterize the microstructure and determine some mechanical properties of a polymer-ingfiltrated ceramic-network (PICN) material (Vita Enamic, Vita Zahnfabrik) available for CAD–CAM systems. Methods Specimens were fabricated to perform quantitative and qualitative analyses of the material’s microstructure and to determine the fracture toughness (KIc), density (ρ), Poisson’s ratio (v) and Young’s modulus (E). KIc was determined using V-notched specimens and the short beam toughness method, where bar-shaped specimens were notched and 3-point loaded to fracture. ρ was calculated using Archimedes principle, and v and E were measured using an ultrasonic thickness gauge with a combination of a pulse generator and an oscilloscope. Results Microstructural analyses showed a ceramic- and a polymer-based interpenetrating network. Mean and standard deviation values for the properties evaluated were: KIc = 1.09 ± 0.05 MPa m1/2, ρ = 2.09 ± 0.01 g/cm3, v = 0.23 ± 0.002 and E = 37.95 ± 0.34 GPa. Significance The PICN material showed mechanical properties between porcelains and resin-based composites, reflecting its microstructural components. PMID:24656471

Characterization of a polymer-infiltrated ceramic-network material.

PubMed

Della Bona, Alvaro; Corazza, Pedro H; Zhang, Yu

2014-05-01

To characterize the microstructure and determine some mechanical properties of a polymer-infiltrated ceramic-network (PICN) material (Vita Enamic, Vita Zahnfabrik) available for CAD-CAM systems. Specimens were fabricated to perform quantitative and qualitative analyses of the material's microstructure and to determine the fracture toughness (KIc), density (ρ), Poisson's ratio (ν) and Young's modulus (E). KIc was determined using V-notched specimens and the short beam toughness method, where bar-shaped specimens were notched and 3-point loaded to fracture. ρ was calculated using Archimedes principle, and ν and E were measured using an ultrasonic thickness gauge with a combination of a pulse generator and an oscilloscope. Microstructural analyses showed a ceramic- and a polymer-based interpenetrating network. Mean and standard deviation values for the properties evaluated were: KIc=1.09±0.05MPam(1/2), ρ=2.09±0.01g/cm(3), ν=0.23±0.002 and E=37.95±0.34GPa. The PICN material showed mechanical properties between porcelains and resin-based composites, reflecting its microstructural components. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Shear History Extensional Rheology Experiment: A Proposed ISS Experiment

NASA Technical Reports Server (NTRS)

Hall, Nancy R.; Logsdon, Kirk A.; Magee, Kevin S.

2007-01-01

The Shear History Extensional Rheology Experiment (SHERE) is a proposed International Space Station (ISS) glovebox experiment designed to study the effect of preshear on the transient evolution of the microstructure and viscoelastic tensile stresses for monodisperse dilute polymer solutions. Collectively referred to as Boger fluids, these polymer solutions have become a popular choice for rheological studies of non-Newtonian fluids and are the non-Newtonian fluid used in this experiment. The SHERE hardware consists of the Rheometer, Camera Arm, Interface Box, Cabling, Keyboard, Tool Box, Fluid Modules, and Stowage Tray. Each component will be described in detail in this paper. In the area of space exploration, the development of in-situ fabrication and repair technology represents a critical element in evolution of autonomous exploration capability. SHERE has the capability to provide data for engineering design tools needed for polymer parts manufacturing systems to ensure their rheological properties have not been impacted in the variable gravity environment and this will be briefly addressed.

Molecular Engineering for Mechanically Resilient and Stretchable Electronic Polymers and Composites

DTIC Science & Technology

2016-06-08

conjugated polymers and composites by analysis of the structural determinants of the mechanical properties. We developed coarse-grained molecular...dynamics simulations that predicted the mechanical properties of conjugated polymers and polymer -fullerene composites. We elucidated the mechanical...We also determined the effect of cyclic stretching on the microstructure and mechanical properties of conjugated polymers . We used many of

Role of Near Substrate and Bulk Polymer Morphology on Out-of-Plane Space-Charge Limited Hole Mobility.

PubMed

Turner, Johnathan; Gadisa, Abay

2016-12-07

Charge transport is a central issue in all types of organic electronic devices. In organic films, charge transport is crucially limited by film microstructure and the nature of the substrate/organic interface interactions. In this report, we discuss the influence of active layer thickness on space-charge limited hole transport in pristine polymer and polymer/fullerene bulk heterojunction thin films (∼15-300 nm) in a diode structure. According to the results, the out-of-plane hole mobility in pristine polymers is sensitive to the degree of polymer chain aggregation. Blending the polymers with a fullerene molecule does not change the trend of hole mobility if the polymer tends to make an amorphous structure. However, employing an aggregating polymer in a bulk heterojunction blend gives rise to a marked difference in charge carrier transport behavior compared to the pristine polymer and this difference is sensitive to active layer thickness. In aggregating polymer films, the thickness-dependent interchain interaction was found to have direct impact on hole mobility. The thickness-dependent mobility trend was found to correspond well with the trend of fill factors of corresponding bulk heterojunction solar cells. This investigation has a vital implication for material design and the development of efficient organic electronic devices, including solar cells and light-emitting diodes.

Highly tunable birefringent microstructured optical fiber.

PubMed

Kerbage, C; Steinvurzel, P; Reyes, P; Westbrook, P S; Windeler, R S; Hale, A; Eggleton, B J

2002-05-15

We demonstrate a method for introducing and dynamically tuning birefringence in a microstructured optical fiber. Waveguide asymmetry in the fiber is obtained by selective filling of air holes with polymer, and tunability is achieved by temperature tuning of the polymer's index. The fiber is tapered such that the mode field expands into the cladding and efficiently overlaps the polymer that has been infused into the air holes, ensuring enhanced tunability and low splice loss. Experimental results are compared with numerical simulations made with the beam propagation method and confirm birefringence tuning that corresponds to a phase change of 6pi for a 1-cm length of fiber.

Bioinspired synthesis of calcium carbonate hollow spheres with a nacre-type laminated microstructure.

PubMed

Dong, Wenyong; Cheng, Haixing; Yao, Yuan; Zhou, Yongfeng; Tong, Gangsheng; Yan, Deyue; Lai, Yijian; Li, Wei

2011-01-04

In this Article, we combine the characters of hyperbranched polymers and the concept of double-hydrophilic block copolymer (DHBC) to design a 3D crystal growth modifier, HPG-COOH. The novel modifier can efficiently control the crystallization of CaCO(3) from amorphous nanoparticles to vaterite hollow spheres by a nonclassical crystallization process. The obtained vaterite hollow spheres have a special puffy dandelion-like appearance; that is, the shell of the hollow spheres is constructed by platelet-like vaterite mesocrystals, perpendicular to the globe surface. The cross-section of the wall of a vaterite hollow sphere is similar to that of nacres in microstructure, in which platelet-like calcium carbonate mesocrystals pile up with one another. These results reveal the topology effect of the crystal growth modifier on biomineralization and the essential role of the nonclassical crystallization for constructing hierarchical microstructures.

Microcontact Printing via a Polymer-Induced Liquid-Precursor (PILP) Process

DTIC Science & Technology

2002-04-01

applications that require high performance mechanical, electrical and/or optical properties resulting from controlled nano- and microstructural design...salts. The cover-slips were examined by optical microscopy, and then gold coated for scanning electron microscopy on a SEM JEOL JSM 6400 instrument [5...applications in the realm of biomimicry . Controlled growth of crystals with specific orientation can be achieved via the functional groups on the substrate

The development and characterization of stimuli-responsive systems for performance materials

NASA Astrophysics Data System (ADS)

Gordon, Melissa B.

In nature, living organisms adjust to their surroundings by responding to environmental cues, such as light, temperature or force. Stimuli-triggered processes, such as the contraction of eyes in response to bright light or wound healing in skin after a cut, motivate the design of "smart" materials which are designed to respond to environmental stimuli. Responsive materials are used as self-healing materials, shape memory polymers and responsive coatings; moreover, responsive materials may also be employed as model systems, which enhance understanding of complex behavior. The overall goal of this work is to design a material that offers self-healing functionality, which will allow for self-repair following material fatigue or failure, and increased strength in response to ballistic or puncture threats through the incorporation of colloidal particles. The target application for this material is as a protective barrier in extreme environments, such as outer space. Towards this end, the dissertation is focused on the development and characterization of each component of the protective material by (1) designing and testing novel light- and force-sensitive polymers for self-healing applications and (2) examining and characterizing long-time behavior (i.e., aging) in model thermoreversible colloidal gels and glasses. Towards the development of novel stimuli-responsive materials, a photo-responsive polymer network is developed in which a dynamic bond is incorporated into the network architecture to enable a light-triggered, secondary polymerization, which increases the modulus by two orders of magnitude while strengthening the network by over 100%. Unlike traditional two-stage polymerization systems, in which the secondary polymerization is triggered by a leachable photoinitiator, the dynamic nature is imparted by the material itself via the dissociation of its own crosslinks to become stronger in response to light. Several attributes of the photo-responsive network are shown including: (1) photo-induced healing and strengthening of a specimen after it has been severed, (2) photopatterning for effecting spatially confined property changes on demand, and (3) locking in the film's 3D geometry using light after reshaping. The utility of the photo-responsive dynamic bond is enhanced by demonstrating that it is also responsive to mechanical force. Force-responsive materials are activated by the energy from the damage event itself, thereby enabling healing without human intervention. Specifically, selective cleavage of a polymer containing a dynamic trithiocarbonate group initiates a force-driven radical polymerization, thus enabling the material to constructively respond to force via gelation on an experimentally relevant timescale. To enhance the stress response of the self-healing materials described above, a protective material composed of colloidal particles is proposed. Toward this goal, the second half of this dissertation investigates the microstructural basis of rheological aging in colloidal gels and glasses using a model thermoreversible colloidal dispersion. In this work, rheological aging is quantitatively related to microstructural aging in glasses and gels by simultaneously measuring the bulk properties and sample microstructure using rheometry and small angle neutron scattering (Rheo-SANS), respectively. A one-to-one correspondence between the evolution in storage modulus and microstructure as the sample ages is observed, which is investigated as a function of thermal and shear history. The microstructural measurements are consistent with the hypothesis of aging as a trajectory in a free energy landscape, which combined with analysis with mode coupling theory, support local particle rearrangements as the mechanism of aging. Moreover, by using a system that is fully rejuvenated by thermal cycling, the effectiveness of shear as a rejuvenation method is investigated by directly comparing microstructure and bulk properties following thermal and mechanical rejuvenation. The conclusions of this study may be industrially relevant to products that age on commercial timescales, such as pharmaceuticals, applicable to other dynamically arrested systems, such as metallic glasses, and provide pathways to advanced composite materials such as those envisioned in this work.

Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out?

PubMed

Kanimozhi, Catherine; Yaacobi-Gross, Nir; Burnett, Edmund K; Briseno, Alejandro L; Anthopoulos, Thomas D; Salzner, Ulrike; Patil, Satish

2014-08-28

The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of side-chains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential "edge-on" packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of >1 cm(2) V(-1) s(-1) were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast, moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.

Fabrication, Densification, and Replica Molding of 3D Carbon Nanotube Microstructures

PubMed Central

Copic, Davor; Park, Sei Jin; Tawfick, Sameh; De Volder, Michael; Hart, A. John

2012-01-01

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip devices, and their applications. In particular, capabilities for cost-effective fabrication of polymer microstructures were transformed by the advent of soft lithography and other micromolding techniques 1, 2, and this led a revolution in applications of microfabrication to biomedical engineering and biology. Nevertheless, it remains challenging to fabricate microstructures with well-defined nanoscale surface textures, and to fabricate arbitrary 3D shapes at the micro-scale. Robustness of master molds and maintenance of shape integrity is especially important to achieve high fidelity replication of complex structures and preserving their nanoscale surface texture. The combination of hierarchical textures, and heterogeneous shapes, is a profound challenge to existing microfabrication methods that largely rely upon top-down etching using fixed mask templates. On the other hand, the bottom-up synthesis of nanostructures such as nanotubes and nanowires can offer new capabilities to microfabrication, in particular by taking advantage of the collective self-organization of nanostructures, and local control of their growth behavior with respect to microfabricated patterns. Our goal is to introduce vertically aligned carbon nanotubes (CNTs), which we refer to as CNT "forests", as a new microfabrication material. We present details of a suite of related methods recently developed by our group: fabrication of CNT forest microstructures by thermal CVD from lithographically patterned catalyst thin films; self-directed elastocapillary densification of CNT microstructures; and replica molding of polymer microstructures using CNT composite master molds. In particular, our work shows that self-directed capillary densification ("capillary forming"), which is performed by condensation of a solvent onto the substrate with CNT microstructures, significantly increases the packing density of CNTs. This process enables directed transformation of vertical CNT microstructures into straight, inclined, and twisted shapes, which have robust mechanical properties exceeding those of typical microfabrication polymers. This in turn enables formation of nanocomposite CNT master molds by capillary-driven infiltration of polymers. The replica structures exhibit the anisotropic nanoscale texture of the aligned CNTs, and can have walls with sub-micron thickness and aspect ratios exceeding 50:1. Integration of CNT microstructures in fabrication offers further opportunity to exploit the electrical and thermal properties of CNTs, and diverse capabilities for chemical and biochemical functionalization 3. PMID:22806089

Fabrication, densification, and replica molding of 3D carbon nanotube microstructures.

PubMed

Copic, Davor; Park, Sei Jin; Tawfick, Sameh; De Volder, Michael; Hart, A John

2012-07-02

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip devices, and their applications. In particular, capabilities for cost-effective fabrication of polymer microstructures were transformed by the advent of soft lithography and other micromolding techniques (1, 2), and this led a revolution in applications of microfabrication to biomedical engineering and biology. Nevertheless, it remains challenging to fabricate microstructures with well-defined nanoscale surface textures, and to fabricate arbitrary 3D shapes at the micro-scale. Robustness of master molds and maintenance of shape integrity is especially important to achieve high fidelity replication of complex structures and preserving their nanoscale surface texture. The combination of hierarchical textures, and heterogeneous shapes, is a profound challenge to existing microfabrication methods that largely rely upon top-down etching using fixed mask templates. On the other hand, the bottom-up synthesis of nanostructures such as nanotubes and nanowires can offer new capabilities to microfabrication, in particular by taking advantage of the collective self-organization of nanostructures, and local control of their growth behavior with respect to microfabricated patterns. Our goal is to introduce vertically aligned carbon nanotubes (CNTs), which we refer to as CNT "forests", as a new microfabrication material. We present details of a suite of related methods recently developed by our group: fabrication of CNT forest microstructures by thermal CVD from lithographically patterned catalyst thin films; self-directed elastocapillary densification of CNT microstructures; and replica molding of polymer microstructures using CNT composite master molds. In particular, our work shows that self-directed capillary densification ("capillary forming"), which is performed by condensation of a solvent onto the substrate with CNT microstructures, significantly increases the packing density of CNTs. This process enables directed transformation of vertical CNT microstructures into straight, inclined, and twisted shapes, which have robust mechanical properties exceeding those of typical microfabrication polymers. This in turn enables formation of nanocomposite CNT master molds by capillary-driven infiltration of polymers. The replica structures exhibit the anisotropic nanoscale texture of the aligned CNTs, and can have walls with sub-micron thickness and aspect ratios exceeding 50:1. Integration of CNT microstructures in fabrication offers further opportunity to exploit the electrical and thermal properties of CNTs, and diverse capabilities for chemical and biochemical functionalization (3).

Dry friction of microstructured polymer surfaces inspired by snake skin.

PubMed

Baum, Martina J; Heepe, Lars; Fadeeva, Elena; Gorb, Stanislav N

2014-01-01

The microstructure investigated in this study was inspired by the anisotropic microornamentation of scales from the ventral body side of the California King Snake (Lampropeltis getula californiae). Frictional properties of snake-inspired microstructured polymer surface (SIMPS) made of epoxy resin were characterised in contact with a smooth glass ball by a microtribometer in two perpendicular directions. The SIMPS exhibited a considerable frictional anisotropy: Frictional coefficients measured along the microstructure were about 33% lower than those measured in the opposite direction. Frictional coefficients were compared to those obtained on other types of surface microstructure: (i) smooth ones, (ii) rough ones, and (iii) ones with periodic groove-like microstructures of different dimensions. The results demonstrate the existence of a common pattern of interaction between two general effects that influence friction: (1) molecular interaction depending on real contact area and (2) the mechanical interlocking of both contacting surfaces. The strongest reduction of the frictional coefficient, compared to the smooth reference surface, was observed at a medium range of surface structure dimensions suggesting a trade-off between these two effects.

Fluoropolymer Microstructure and Dynamics: Influence of Molecular Orientation Induced by Uniaxial Drawing

NASA Astrophysics Data System (ADS)

Miranda, Daniel; Yin, Chaoqing; Runt, James

Fluorinated semi-crystalline polymer films are attractive for dielectric film applications due to their chemical inertness, heat resistance, and high thermal stability. In the present investigation we explore the influence of orientation induced by uniaxial drawing on the crystalline microstructure and relaxation processes of poly(ethylene-tetrafluoroethylene) (ETFE), in order to ascertain how morphological control can benefit polymer dielectric design. When drawn below or near the Tg, the crystallinity of the drawn films is unchanged, and oriented amorphous structures and crystalline microfibrils form at high draw ratios. This orientation slows segmental relaxation, reflected by an increase in the dynamic Tg, and also delays the transition to the high temperature crystalline form of ETFE. When drawing above the Tg, the films undergo strain-induced crystallization at high draw ratios. For these films an increase in the dynamic Tg is also observed, in addition to a second segmental relaxation process, appearing as a shoulder on the primary process. We propose that this represents a contribution from a rigid amorphous fraction, having slowed chain dynamics. Supported by Office of Naval Research.

Modular-based multiscale modeling on viscoelasticity of polymer nanocomposites

NASA Astrophysics Data System (ADS)

Li, Ying; Liu, Zeliang; Jia, Zheng; Liu, Wing Kam; Aldousari, Saad M.; Hedia, Hassan S.; Asiri, Saeed A.

2017-02-01

Polymer nanocomposites have been envisioned as advanced materials for improving the mechanical performance of neat polymers used in aerospace, petrochemical, environment and energy industries. With the filler size approaching the nanoscale, composite materials tend to demonstrate remarkable thermomechanical properties, even with addition of a small amount of fillers. These observations confront the classical composite theories and are usually attributed to the high surface-area-to-volume-ratio of the fillers, which can introduce strong nanoscale interfacial effect and relevant long-range perturbation on polymer chain dynamics. Despite decades of research aimed at understanding interfacial effect and improving the mechanical performance of composite materials, it is not currently possible to accurately predict the mechanical properties of polymer nanocomposites directly from their molecular constituents. To overcome this challenge, different theoretical, experimental and computational schemes will be used to uncover the key physical mechanisms at the relevant spatial and temporal scales for predicting and tuning constitutive behaviors in silico, thereby establishing a bottom-up virtual design principle to achieve unprecedented mechanical performance of nanocomposites. A modular-based multiscale modeling approach for viscoelasticity of polymer nanocomposites has been proposed and discussed in this study, including four modules: (A) neat polymer toolbox; (B) interphase toolbox; (C) microstructural toolbox and (D) homogenization toolbox. Integrating these modules together, macroscopic viscoelasticity of polymer nanocomposites could be directly predicted from their molecular constituents. This will maximize the computational ability to design novel polymer composites with advanced performance. More importantly, elucidating the viscoelasticity of polymer nanocomposites through fundamental studies is a critical step to generate an integrated computational material engineering principle for discovering and manufacturing new composites with transformative impact on aerospace, automobile, petrochemical industries.

Swollen poly(dimethylsiloxane) (PDMS) as a template for inorganic morphologies.

PubMed

Brennan, Daniel P; Dobley, Arthur; Sideris, Paul J; Oliver, Scott R J

2005-12-06

We report a series of silica, titania, and zirconia microstructures synthesized within swollen poly(dimethylsiloxane) (PDMS). Voids created by solvent-swelling the polymer are used to template the product. The inorganic morphologies range from spheres to networks, depending upon the nature of the polymer, its degree of swelling, and the synthetic conditions. Organic solvents as well as pure metal alkoxide liquids have been used to swell the polymer. Once the alkoxide precursor is inside the swollen polymer, water is introduced to bring about hydrolysis and condensation polymerization. The product is a textured metal oxide within a PDMS matrix. Scanning electron microscopy (SEM), optical microscopy, nuclear magnetic resonance (NMR), and powder X-ray diffraction (PXRD) were used to characterize the products. Microstructures formed in this manner have potential use as an inexpensive route to catalysts, fillers, capsules, or membranes for separations.

Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites.

PubMed

Zhang, Lin; Shan, Xiaobing; Bass, Patrick; Tong, Yang; Rolin, Terry D; Hill, Curtis W; Brewer, Jeffrey C; Tucker, Dennis S; Cheng, Z-Y

2016-10-21

Influences of process conditions on microstructure and dielectric properties of ceramic-polymer composites are systematically studied using CaCu 3 Ti 4 O 12 (CCTO) as filler and P(VDF-TrFE) 55/45 mol.% copolymer as the matrix by combining solution-cast and hot-pressing processes. It is found that the dielectric constant of the composites can be significantly enhanced-up to about 10 times - by using proper processing conditions. The dielectric constant of the composites can reach more than 1,000 over a wide temperature range with a low loss (tan δ ~ 10 -1 ). It is concluded that besides the dense structure of composites, the uniform distribution of the CCTO particles in the matrix plays a key role on the dielectric enhancement. Due to the influence of the CCTO on the microstructure of the polymer matrix, the composites exhibit a weaker temperature dependence of the dielectric constant than the polymer matrix. Based on the results, it is also found that the loss of the composites at low temperatures, including room temperature, is determined by the real dielectric relaxation processes including the relaxation process induced by the mixing.

Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites

NASA Astrophysics Data System (ADS)

Zhang, Lin; Shan, Xiaobing; Bass, Patrick; Tong, Yang; Rolin, Terry D.; Hill, Curtis W.; Brewer, Jeffrey C.; Tucker, Dennis S.; Cheng, Z.-Y.

2016-10-01

Influences of process conditions on microstructure and dielectric properties of ceramic-polymer composites are systematically studied using CaCu3Ti4O12 (CCTO) as filler and P(VDF-TrFE) 55/45 mol.% copolymer as the matrix by combining solution-cast and hot-pressing processes. It is found that the dielectric constant of the composites can be significantly enhanced-up to about 10 times - by using proper processing conditions. The dielectric constant of the composites can reach more than 1,000 over a wide temperature range with a low loss (tan δ ~ 10-1). It is concluded that besides the dense structure of composites, the uniform distribution of the CCTO particles in the matrix plays a key role on the dielectric enhancement. Due to the influence of the CCTO on the microstructure of the polymer matrix, the composites exhibit a weaker temperature dependence of the dielectric constant than the polymer matrix. Based on the results, it is also found that the loss of the composites at low temperatures, including room temperature, is determined by the real dielectric relaxation processes including the relaxation process induced by the mixing.

Process and Microstructure to Achieve Ultra-high Dielectric Constant in Ceramic-Polymer Composites

PubMed Central

Zhang, Lin; Shan, Xiaobing; Bass, Patrick; Tong, Yang; Rolin, Terry D.; Hill, Curtis W.; Brewer, Jeffrey C.; Tucker, Dennis S.; Cheng, Z.-Y.

2016-01-01

Influences of process conditions on microstructure and dielectric properties of ceramic-polymer composites are systematically studied using CaCu3Ti4O12 (CCTO) as filler and P(VDF-TrFE) 55/45 mol.% copolymer as the matrix by combining solution-cast and hot-pressing processes. It is found that the dielectric constant of the composites can be significantly enhanced–up to about 10 times – by using proper processing conditions. The dielectric constant of the composites can reach more than 1,000 over a wide temperature range with a low loss (tan δ ~ 10−1). It is concluded that besides the dense structure of composites, the uniform distribution of the CCTO particles in the matrix plays a key role on the dielectric enhancement. Due to the influence of the CCTO on the microstructure of the polymer matrix, the composites exhibit a weaker temperature dependence of the dielectric constant than the polymer matrix. Based on the results, it is also found that the loss of the composites at low temperatures, including room temperature, is determined by the real dielectric relaxation processes including the relaxation process induced by the mixing. PMID:27767184

Computer Simulation of Spatial Arrangement and Connectivity of Particles in Three-Dimensional Microstructure: Application to Model Electrical Conductivity of Polymer Matrix Composite

NASA Technical Reports Server (NTRS)

Louis, P.; Gokhale, A. M.

1996-01-01

Computer simulation is a powerful tool for analyzing the geometry of three-dimensional microstructure. A computer simulation model is developed to represent the three-dimensional microstructure of a two-phase particulate composite where particles may be in contact with one another but do not overlap significantly. The model is used to quantify the "connectedness" of the particulate phase of a polymer matrix composite containing hollow carbon particles in a dielectric polymer resin matrix. The simulations are utilized to estimate the morphological percolation volume fraction for electrical conduction, and the effective volume fraction of the particles that actually take part in the electrical conduction. The calculated values of the effective volume fraction are used as an input for a self-consistent physical model for electrical conductivity. The predicted values of electrical conductivity are in very good agreement with the corresponding experimental data on a series of specimens having different particulate volume fraction.

Solution Adsorption Formation of a π-Conjugated Polymer/Graphene Composite for High-Performance Field-Effect Transistors.

PubMed

Liu, Yun; Hao, Wei; Yao, Huiying; Li, Shuzhou; Wu, Yuchen; Zhu, Jia; Jiang, Lei

2018-01-01

Semiconducting polymers with π-conjugated electronic structures have potential application in the large-scale printable fabrication of high-performance electronic and optoelectronic devices. However, owing to their poor environmental stability and high-cost synthesis, polymer semiconductors possess limited device implementation. Here, an approach for constructing a π-conjugated polymer/graphene composite material to circumvent these limitations is provided, and then this material is patterned into 1D arrays. Driven by the π-π interaction, several-layer polymers can be adsorbed onto the graphene planes. The low consumption of the high-cost semiconductor polymers and the mass production of graphene contribute to the low-cost fabrication of the π-conjugated polymer/graphene composite materials. Based on the π-conjugated system, a reduced π-π stacking distance between graphene and the polymer can be achieved, yielding enhanced charge-transport properties. Owing to the incorporation of graphene, the composite material shows improved thermal stability. More generally, it is believed that the construction of the π-conjugated composite shows clear possibility of integrating organic molecules and 2D materials into microstructure arrays for property-by-design fabrication of functional devices with large area, low cost, and high efficiency. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interbody fusion cage design using integrated global layout and local microstructure topology optimization.

PubMed

Lin, Chia-Ying; Hsiao, Chun-Ching; Chen, Po-Quan; Hollister, Scott J

2004-08-15

An approach combining global layout and local microstructure topology optimization was used to create a new interbody fusion cage design that concurrently enhanced stability, biofactor delivery, and mechanical tissue stimulation for improved arthrodesis. To develop a new interbody fusion cage design by topology optimization with porous internal architecture. To compare the performance of this new design to conventional threaded cage designs regarding early stability and long-term stress shielding effects on ingrown bone. Conventional interbody cage designs mainly fall into categories of cylindrical or rectangular shell shapes. The designs contribute to rigid stability and maintain disc height for successful arthrodesis but may also suffer mechanically mediated failures of dislocation or subsidence, as well as the possibility of bone resorption. The new optimization approach created a cage having designed microstructure that achieved desired mechanical performance while providing interconnected channels for biofactor delivery. The topology optimization algorithm determines the material layout under desirable volume fraction (50%) and displacement constraints favorable to bone formation. A local microstructural topology optimization method was used to generate periodic microstructures for porous isotropic materials. Final topology was generated by the integration of the two-scaled structures according to segmented regions and the corresponding material density. Image-base finite element analysis was used to compare the mechanical performance of the topology-optimized cage and conventional threaded cage. The final design can be fabricated by a variety of Solid Free-Form systems directly from the image output. The new design exhibited a narrower, more uniform displacement range than the threaded cage design and lower stress at the cage-vertebra interface, suggesting a reduced risk of subsidence. Strain energy density analysis also indicated that a higher portion of total strain energy density was transferred into the new bone region inside the new designed cage, indicating a reduced risk of stress shielding. The new design approach using integrated topology optimization demonstrated comparable or better stability by limited displacement and reduced localized deformation related to the risk of subsidence. Less shielding of newly formed bone was predicted inside the new designed cage. Using the present approach, it is also possible to tailor cage design for specific materials, either titanium or polymer, that can attain the desired balance between stability, reduced stress shielding, and porosity for biofactor delivery.

Controlled growth of Au nanoparticles in co-evaporated metal/polymer composite films and their optical and electrical properties

NASA Astrophysics Data System (ADS)

Takele, H.; Schürmann, U.; Greve, H.; Paretkar, D.; Zaporojtchenko, V.; Faupel, F.

2006-02-01

Nanocomposite films containing Au nanoparticles embedded in a polymer matrix were prepared by vapour phase co-deposition of Au and polymers (Teflon AF and Poly(α -methylstyrene)) in high vacuum. The microstructure of the composite materials as well as metal content strongly depend on the condensation coefficient of the Au atoms, the deposition rates of the components, the substrate temperature, and the type of polymer matrix. The condensation coefficient, which varies between 0.03 and 1, was determined from energy dispersive X-ray spectrometer (EDX) and surface profilometry. It is shown that the microstructure of nanocomposites (size, size distribution, and interparticle separation of metal clusters), which was determined by transmission electron microscopy, can be controlled by the deposition parameters and the choice of polymer matrix. The optical absorption in the visible region due to the particle plasmon resonance has a strong dependence on the metal filling factor. The correlation between the microstructure of nanocomposites and optical properties, studied using UV-Vis spectroscopy, was also established. Further more, the electrical properties of the composites were studied as a function of the metal volume fraction. It was observed that the nanocomposite films exhibit a percolation threshold at a metal volume fraction of 0.43 and 0.20 for gold nanoclusters in Teflon AF and Poly(α-methylstyrene), respectively.

Chasing Extreme Polymer Morphologies with Ed

NASA Astrophysics Data System (ADS)

Fredrickson, Glenn

I was privileged to have a seventeen year friendship and scientific collaboration with Edward J. Kramer that produced 55 papers and countless student and postdoc co-advisements. This talk will discuss our last project together; an ongoing research program to achieve thermoplastic polymer materials that are uniquely hard, tough, and elastic, with moduli greater than 100 MPa and elastic recovery greater than 0.9 at strains of 1 or more. The targeted materials are based on an A(BA')n mikto-arm block copolymer architecture, and alloys of these molecules with A homopolymer. The molecular design of the miktopolymer was optimized using self-consistent field theory and the materials realized in a polystyrene (A)-polyisoprene (B) system. TEM, SAXS, and tensile mechanical tests were used to validate the designs and probe microstructure/mechanics relationships. An unexpected discovery was the emergence of a new structured disordered phase - the bricks and mortar phase -in which the A domains remain discrete at up to a volume fraction of 0.7. Field-theoretic simulations have been used to understand the origins of this new fluctuation-stabilized equilibrium phase, which has no precedent in the polymer physics literature.

Auto-Origami and Soft Programmable Transformers: Simulation Studies of Liquid Crystal Elastomers and Swelling Polymer Gels

NASA Astrophysics Data System (ADS)

Konya, Andrew; Santangelo, Christian; Selinger, Robin

2014-03-01

When the underlying microstructure of an actuatable material varies in space, simple sheets can transform into complex shapes. Using nonlinear finite element elastodynamic simulations, we explore the design space of two such materials: liquid crystal elastomers and swelling polymer gels. Liquid crystal elastomers (LCE) undergo shape transformations induced by stimuli such as heating/cooling or illumination; complex deformations may be programmed by ``blueprinting'' a non-uniform director field in the sample when the polymer is cross-linked. Similarly, swellable gels can undergo shape change when they are swollen anisotropically as programmed by recently developed halftone gel lithography techniques. For each of these materials we design and test programmable motifs which give rise to complex deformation trajectories including folded structures, soft swimmers, apertures that open and close, bas relief patterns, and other shape transformations inspired by art and nature. In order to accommodate the large computational needs required to model these materials, our 3-d nonlinear finite element elastodynamics simulation algorithm is implemented in CUDA, running on a single GPU-enabled workstation.

Inter-Fullerene Electronic Coupling Controls the Efficiency of Photoinduced Charge Generation in Organic Bulk Heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larson, Bryon W.; Reid, Obadiah G.; Coffey, David C.

2016-09-26

Photoinduced charge generation (PCG) dynamics are notoriously difficult to correlate with specific molecular properties in device relevant polymer:fullerene organic photovoltaic blend films due to the highly complex nature of the solid state blend morphology. Here, this study uses six judiciously selected trifluoromethylfullerenes blended with the prototypical polymer poly(3-hexylthiophene) and measure the PCG dynamics in 50 fs-500 ns time scales with time-resolved microwave conductivity and femtosecond transient absorption spectroscopy. The isomeric purity and thorough chemical characterization of the fullerenes used in this study allow for a detailed correlation between molecular properties, driving force, local intermolecular electronic coupling and, ultimately, the efficiencymore » of PCG yield. The findings show that the molecular design of the fullerene not only determines inter-fullerene electronic coupling, but also influences the decay dynamics of free holes in the donor phase even when the polymer microstructure remains unchanged.« less

Multi-Length Scale-Enriched Continuum-Level Material Model for Kevlar-Fiber-Reinforced Polymer-Matrix Composites

DTIC Science & Technology

2012-08-03

is unlimited. Multi-Length Scale-Enriched Continuum-Level Material Model for Kevlar ®-Fiber-Reinforced Polymer-Matrix Composites The views, opinions...12211 Research Triangle Park, NC 27709-2211 ballistics, composites, Kevlar , material models, microstructural defects REPORT DOCUMENTATION PAGE 11... Kevlar ®-Fiber-Reinforced Polymer-Matrix Composites Report Title Fiber-reinforced polymer matrix composite materials display quite complex deformation

An Insilico Design of Nanoclay Based Nanocomposites and Scaffolds in Bone Tissue Engineering

NASA Astrophysics Data System (ADS)

Sharma, Anurag

A multiscale in silico approach to design polymer nanocomposites and scaffolds for bone tissue engineering applications is described in this study. This study focuses on the role of biomaterials design and selection, structural integrity and mechanical properties evolution during degradation and tissue regeneration in the successful design of polymer nanocomposite scaffolds. Polymer nanocomposite scaffolds are synthesized using aminoacid modified montmorillonite nanoclay with biomineralized hydroxyapatite and polycaprolactone (PCL/in situ HAPclay). Representative molecular models of polymer nanocomposite system are systematically developed using molecular dynamics (MD) technique and successfully validated using material characterization techniques. The constant force steered molecular dynamics (fSMD) simulation results indicate a two-phase nanomechanical behavior of the polymer nanocomposite. The MD and fSMD simulations results provide quantitative contributions of molecular interactions between different constituents of representative models and their effect on nanomechanical responses of nanoclay based polymer nanocomposite system. A finite element (FE) model of PCL/in situ HAPclay scaffold is built using micro-computed tomography images and bridging the nanomechanical properties obtained from fSMD simulations into the FE model. A new reduction factor, K is introduced into modeling results to consider the effect of wall porosity of the polymer scaffold. The effect of accelerated degradation under alkaline conditions and human osteoblast cells culture on the evolution of mechanical properties of scaffolds are studied and the damage mechanics based analytical models are developed. Finally, the novel multiscale models are developed that incorporate the complex molecular and microstructural properties, mechanical properties at nanoscale and structural levels and mechanical properties evolution during degradation and tissue formation in the polymer nanocomposite scaffold. Overall, this study provides a leap into methodologies for in silico design of biomaterials for bone tissue engineering applications. Furthermore, as a part of this work, a molecular dynamics study of rice DNA in the presence of single walled carbon nanotube is carried out to understand the role played by molecular interactions in the conformation changes of rice DNA. The simulations results showed wrapping of DNA onto SWCNT, breaking and forming of hydrogen bonds due to unzipping of Watson-Crick (WC) nucleobase pairs and forming of new non-WC nucleobase pairs in DNA.

A novel surface imprinted polymer/magnetic hydroxyapatite nanocomposite for selective dibenzothiophene scavenging

NASA Astrophysics Data System (ADS)

Ali, Hager R.; El-Maghrabi, Heba H.; Zahran, Fouad; Moustafa, Yasser Mohamed

2017-12-01

Highly selective adsorbent for dibenzothiophene (DBT) was successfully designed and prepared. Molecularly imprinted polymer (MIP) and magnetic hydroxyapatite (MHAP) were used as building blocks for the novel nanocomposite adsorbent. MIP/MHAP was synthesized by grafting polymerization and surface molecular imprinting using DBT as a template molecule. The microstructure and morphology of the designed nanoadsorbent were examined via FTIR, SEM and VSM. Specific surface area and pore size distribution were determined by Quantachrome Nova 3200S automated gas sorption apparatus. Additionally, static adsorption experiments, isotherms and selective recognition adsorption studies were carried out. Reversed-phase high performance liquid chromatography (RP-HPLC) was used to determine DBT. The experimental data exhibits excellent adsorption capacity for DBT reaches 247 mg/g within 60 min. Competitive adsorption results proved that MIP/MHAP have a greater affinity towards DBT molecules than benzothiophene analogues. Pseudo-second-order model and the Langmuir isotherm were used to describe the adsorption process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laguna, O.; Collar, E.P.; Taranco, J.

Observations are made about microstructural aspects from HDPE and LDPE homopolymers and their blends as virgin materials and also from urban plastic wastes. Micrographs were taken by SEM. Micrographs corresponding to the fracture surface from specimens tested in an impact test clearly show different microstructural features due to polymer which is more than 50%. Parts were injection molded. A discussion is given about crystallization behavior of those materials obtained by DSC. For all blends the same results have been found, i.e., two peaks owing to each of the two polymers which are present in the blends.

A Combined Experimental and Numerical Approach to the Laser Joining of Hybrid Polymer - Metal Parts

NASA Astrophysics Data System (ADS)

Rodríguez-Vidal, E.; Lambarri, J.; Soriano, C.; Sanz, C.; Verhaeghe, G.

A two-step method for the joining of opaque polymer to metal is presented. Firstly, the metal is structured locally on a micro-scale level, to ensure adhesion with the polymeric counterpart. In a second step, the opposite side of the micro-structured metal is irradiated by means of a laser source. The heat thereby created is conducted by the metal and results in the melting of the polymer at the interface. The polymer thereby adheres to the metal and flows into the previously engraved structures, creating an additional mechanical interlock between the two materials. The welding parameters are fine-tuned with the assistance of a finite element model, to ensure the required interface temperature. The method is illustrated using a dual phase steel joined to a fiber-reinforced polyamide. The effect of different microstructures, in particular geometry and cavity aspect ratio, on the joint's tensile-shear mechanical performance is discussed.

Ignition probability of polymer-bonded explosives accounting for multiple sources of material stochasticity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, S.; Barua, A.; Zhou, M., E-mail: min.zhou@me.gatech.edu

2014-05-07

Accounting for the combined effect of multiple sources of stochasticity in material attributes, we develop an approach that computationally predicts the probability of ignition of polymer-bonded explosives (PBXs) under impact loading. The probabilistic nature of the specific ignition processes is assumed to arise from two sources of stochasticity. The first source involves random variations in material microstructural morphology; the second source involves random fluctuations in grain-binder interfacial bonding strength. The effect of the first source of stochasticity is analyzed with multiple sets of statistically similar microstructures and constant interfacial bonding strength. Subsequently, each of the microstructures in the multiple setsmore » is assigned multiple instantiations of randomly varying grain-binder interfacial strengths to analyze the effect of the second source of stochasticity. Critical hotspot size-temperature states reaching the threshold for ignition are calculated through finite element simulations that explicitly account for microstructure and bulk and interfacial dissipation to quantify the time to criticality (t{sub c}) of individual samples, allowing the probability distribution of the time to criticality that results from each source of stochastic variation for a material to be analyzed. Two probability superposition models are considered to combine the effects of the multiple sources of stochasticity. The first is a parallel and series combination model, and the second is a nested probability function model. Results show that the nested Weibull distribution provides an accurate description of the combined ignition probability. The approach developed here represents a general framework for analyzing the stochasticity in the material behavior that arises out of multiple types of uncertainty associated with the structure, design, synthesis and processing of materials.« less

Design of Microstructured Conducting Polymer Films for Enhanced Trace Explosives Detection

NASA Astrophysics Data System (ADS)

Laster, Jennifer S.

The detection of trace amounts of explosive material is critical to national security. Ion mobility spectrometer (IMS)-based contact sampling continues to be a common method employed for the detection of explosives in high security checkpoint applications, such as airport security. In this process a surface of interest, such as a passenger's hands or luggage, is probed by a swab or particle trap to collect and transfer residue to an IMS for analysis. The collection of residue on a sampling swab has been shown to be a limiting step in this detection process. As such, there is significant need to develop new materials with increased adhesion to explosive analytes and with superior particle removal abilities. Here, the design of novel sampling swabs is presented for the enhanced collection of trace explosive residue from surfaces. First, the influence of the swab microstructure on the ability to remove particles from representative substrates is demonstrated. Free-standing microstructured polypyrrole (PPy) films of a variety of dimensions and form factors are fabricated using a templated electropolymerization process. The removal of polystyrene fluorescent particles from an aluminum substrate of varying surface roughness is examined as a function of the polymer microstructure. PPy microstructured films display enhanced particle removal abilities compared to PPy non-structured and current commercial films. This increase in particle removal is attributed to the increased particle-swab contact from the microstructured films. Next, the influence of the surface chemistry of sampling swabs on the collection of a representative explosive analyte, trinitrotoluene (TNT) is explored. The surface chemistry of PPy films is modified by electropolymerizaton of an N-substituted pyrrole monomer. The surface chemistries examined include a methyl, carboxylic acid, and amino-phenyl functionality. The vapor deposition of TNT on the surface of the functionalized PPy films is quantified through ultraviolet-visible (UV-vis) absorption and compared to commercial swabbing materials of varying chemistry and surface roughness. The PPy modified films with potential sites for hydrogen bonding display the highest deposition of TNT, while the Teflon coated commercial films display the lowest interaction with TNT. Finally, the desorption and release of TNT from sampling swabs is studied as an effect of temperature and of applied bias. For successful analyte detection within an IMS, the residue collected on a sampling swab must be released from the swab, typically through a thermal desorption process. In this work the release of TNT from sampling swabs is determined through solid-phase microextraction-gas chromatography mass spectrometry (SPME-GCMS). The results of this thesis provide important information on the design considerations for the development of novel particle sampling swabs with increased performance.

Femtosecond-Laser Patterning of Polymers: Nonlinear and Negative Index Devices

DTIC Science & Technology

2011-01-20

LITHOGRAPHY; PHOTOPOLYMERIZATION; MICROSTRUCTURES; NANOPARTICLES; CHITIN ; POLYMERS; BIOMATERIALS; RAMAN SPECTROSCOPY AND SCATTERING; ENHANCED Eric Mazur...cationic polysaccharide obtained by deacetylation of chitin [(1→4)-2 acetamide–2 –deoxy--D-glucan], a structural polysaccharide normally encountered in

Micropunching lithography for generating micro- and submicron-patterns on polymer substrates.

PubMed

Chakraborty, Anirban; Liu, Xinchuan; Luo, Cheng

2012-07-02

Conducting polymers have attracted great attention since the discovery of high conductivity in doped polyacetylene in 1977(1). They offer the advantages of low weight, easy tailoring of properties and a wide spectrum of applications(2,3). Due to sensitivity of conducting polymers to environmental conditions (e.g., air, oxygen, moisture, high temperature and chemical solutions), lithographic techniques present significant technical challenges when working with these materials(4). For example, current photolithographic methods, such as ultra-violet (UV), are unsuitable for patterning the conducting polymers due to the involvement of wet and/or dry etching processes in these methods. In addition, current micro/nanosystems mainly have a planar form(5,6). One layer of structures is built on the top surfaces of another layer of fabricated features. Multiple layers of these structures are stacked together to form numerous devices on a common substrate. The sidewall surfaces of the microstructures have not been used in constructing devices. On the other hand, sidewall patterns could be used, for example, to build 3-D circuits, modify fluidic channels and direct horizontal growth of nanowires and nanotubes. A macropunching method has been applied in the manufacturing industry to create macropatterns in a sheet metal for over a hundred years. Motivated by this approach, we have developed a micropunching lithography method (MPL) to overcome the obstacles of patterning conducting polymers and generating sidewall patterns. Like the macropunching method, the MPL also includes two operations (Fig. 1): (i) cutting; and (ii) drawing. The "cutting" operation was applied to pattern three conducting polymers(4), polypyrrole (PPy), Poly(3,4-ethylenedioxythiophen)-poly(4-styrenesulphonate) (PEDOT) and polyaniline (PANI). It was also employed to create Al microstructures(7). The fabricated microstructures of conducting polymers have been used as humidity(8), chemical(8), and glucose sensors(9). Combined microstructures of Al and conducting polymers have been employed to fabricate capacitors and various heterojunctions(9,10,11). The "cutting" operation was also applied to generate submicron-patterns, such as 100- and 500-nm-wide PPy lines as well as 100-nm-wide Au wires. The "drawing" operation was employed for two applications: (i) produce Au sidewall patterns on high density polyethylene (HDPE) channels which could be used for building 3D microsystems(12,13,14), and (ii) fabricate polydimethylsiloxane (PDMS) micropillars on HDPE substrates to increase the contact angle of the channel(15).

Microstructure Development in Polymers.

DTIC Science & Technology

1981-05-12

J. S. Lin, R. W. Hendricks, J. Petermann , and R. M. Gohil, J. Polymer Sci., Polym. Phys. Ed., 19, 609 (1981). 8. J. Petermann , J. M. Schultz, R. M...Gohil, R. W. Hendricks, and J. S. Lin, submitted to Polymer. 9. J. Rau, R. M. Gohil, J. Petermann , and J. M. Schultz, Colloid & Polymer Sci., 259, 241...1981). 10. J. Petermann , J. M. Schultz, R. W. Hendricks, and J. S. Lin, J. Mater. Sci., 16, 265 (1981). 11. K. M. Gupte, Ph.D. Dissertation, Univ. of

Application of Image Analysis for Characterization of Spatial Arrangements of Features in Microstructure

NASA Technical Reports Server (NTRS)

Louis, Pascal; Gokhale, Arun M.

1995-01-01

A number of microstructural processes are sensitive to the spatial arrangements of features in microstructure. However, very little attention has been given in the past to the experimental measurements of the descriptors of microstructural distance distributions due to the lack of practically feasible methods. We present a digital image analysis procedure to estimate the micro-structural distance distributions. The application of the technique is demonstrated via estimation of K function, radial distribution function, and nearest-neighbor distribution function of hollow spherical carbon particulates in a polymer matrix composite, observed in a metallographic section.

ZT 0.1 Electron-Carrying Polymer Thermoelectric Composites with In Situ SnCl 2 Microstructure Growth (Open Access)

DTIC Science & Technology

2015-05-08

derivatives as potential dopants , [ 21 ] achieving elec- trical conductivities of nearly 0.01 S cm −1 and PF of 0.6 W m −1 K −2 . Segalman and co-workers...Weinheim cobalt (III) acetylacetonate (Co(acac) 3 )) to show more broadly that weakly doping microstructured inclusions can act synergis- tically with...P3 ) and PBTTT-C14 ( P4 ). The weak dopant Co(acac) 3 will form large crystals readily in p-type polymers such as P3 and P4 . S > 2000 µV K

Spatially controlled, in situ synthesis of polymers

DOEpatents

Caneba, Gerard T.; Tirumala, Vijaya Raghavan; Mancini, Derrick C.; Wang, Hsien-Hau

2005-03-22

An in situ polymer microstructure formation method. The monomer mixture is polymerized in a solvent/precipitant through exposure to ionizing radiation in the absence any chemical mediators. If an exposure mask is employed to block out certain regions of the radiation cross section, then a patterned microstructure is formed. The polymerization mechanism is based on the so-called free-radical retrograde-precipitation polymerization process, in which polymerization occurs while the system is phase separating above the lower critical solution temperature. This method was extended to produce a crosslinked line grid-pattern of poly (N-isopropylacrylamide), which has been known to have thermoreversible properties.

Piezoelectric Nanoparticle-Polymer Composite Materials

NASA Astrophysics Data System (ADS)

McCall, William Ray

Herein we demonstrate that efficient piezoelectric nanoparticle-polymer composite materials can be synthesized and fabricated into complex microstructures using sugar-templating methods or optical printing techniques. Stretchable foams with excellent tunable piezoelectric properties are created by incorporating sugar grains directly into polydimethylsiloxane (PDMS) mixtures containing barium titanate (BaTiO3 -- BTO) nanoparticles and carbon nanotubes (CNTs), followed by removal of the sugar after polymer curing. Porosities and elasticity are tuned by simply adjusting the sugar/polymer mass ratio and the electrical performance of the foams showed a direct relationship between porosity and the piezoelectric outputs. User defined 2D and 3D optically printed piezoelectric microstructures are also fabricated by incorporating BTO nanoparticles into photoliable polymer solutions such as polyethylene glycol diacrylate (PEGDA) and exposing to digital optical masks that can be dynamically altered. Mechanical-to-electrical conversion efficiency of the optically printed composite is enhanced by chemically altering the surface of the BTO nanoparticles with acrylate groups which form direct covalent linkages with the polymer matrix under light exposure. Both of these novel materials should find exciting uses in a variety of applications including energy scavenging platforms, nano- and microelectromechanical systems (NEMS/MEMS), sensors, and acoustic actuators.

Impact of electrode preparation on the bending of asymmetric planar electro-active polymer microstructures

NASA Astrophysics Data System (ADS)

Weiss, Florian M.; Töpper, Tino; Osmani, Bekim; Winterhalter, Carla; Müller, Bert

2014-03-01

Compliant electrodes of microstructures have been a research topic for many years because of the increasing interest in consumer electronics, robotics, and medical applications. This interest includes electrically activated polymers (EAP), mainly applied in robotics, lens systems, haptics and foreseen in a variety of medical devices. Here, the electrodes consist of metals such as gold, graphite, conductive polymers or certain composites. The common metal electrodes have been magnetron sputtered, thermally evaporated or prepared using ion implantation. In order to compare the functionality of planar metal electrodes in EAP microstructures, we have investigated the mechanical properties of magnetron sputtered and thermally evaporated electrodes taking advantage of cantilever bending of the asymmetric, rectangular microstructures. We demonstrate that the deflection of the sputtered electrodes is up to 39 % larger than that of thermally evaporated nanometer-thin film on a single silicone film. This difference has even more impact on nanometer-thin, multi-stack, low-voltage EAP actuators. The stiffening effect of many metallic electrode layers is expected to be one of the greatest drawbacks in the multi-stack approaches, which will be even more pronounced if the elastomer layer thickness will be in the sub-micrometer range. Additionally, an improvement in voltage and strain resolution is presented, which is as low as 2 V or 5 × 10-5 above 10 V applied.

Visualization of Hierarchical Nanodomains in Polymer/Fullerene Bulk Heterojunction Solar Cells

DOE PAGES

Wen, Jianguo; Miller, Dean J.; Chen, Wei; ...

2014-06-20

Here, traditional electron microscopy techniques such as bright-field imaging provide poor contrast for organic films and identification of structures in amorphous material can be problematic, particularly in high-performance organic solar cells. By combining energy-filtered corrected transmission electron microscopy, together with electron energy loss and X-ray energy-dispersive hyperspectral imaging, we have imaged PTB7/ PC 61BM blended polymer optical photovoltaic films, and were able to identify domains ranging in size from several hundred nanometers to several nanometers in extent. This work verifies that microstructural domains exist in bulk heterojunctions in PTB7/PC 61BM polymeric solar cells at multiple length scales and expands ourmore » understanding of optimal device performance providing insight for the design of even higher performance cells.« less

Optimization of High Porosity Thermal Barrier Coatings Generated with a Porosity Former

NASA Astrophysics Data System (ADS)

Medřický, Jan; Curry, Nicholas; Pala, Zdenek; Vilemova, Monika; Chraska, Tomas; Johansson, Jimmy; Markocsan, Nicolaie

2015-04-01

Yttria-stabilized zirconia thermal barrier coatings are extensively used in turbine industry; however, increasing performance requirements have begun to make conventional air plasma sprayed coatings insufficient for future needs. Since the thermal conductivity of bulk material cannot be lowered easily; the design of highly porous coatings may be the most efficient way to achieve coatings with low thermal conductivity. Thus the approach of fabrication of coatings with a high porosity level based on plasma spraying of ceramic particles of dysprosia-stabilized zirconia mixed with polymer particles, has been tested. Both polymer and ceramic particles melt in plasma and after impact onto a substrate they form a coating. When the coating is subjected to heat treatment, polymer burns out and a complex structure of pores and cracks is formed. In order to obtain desired porosity level and microstructural features in coatings; a design of experiments, based on changes in spray distance, powder feeding rate, and plasma-forming atmosphere, was performed. Acquired coatings were evaluated for thermal conductivity and thermo-cyclic fatigue, and their morphology was assessed using scanning electron microscopy. It was shown that porosity level can be controlled by appropriate changes in spraying parameters.

A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing

NASA Technical Reports Server (NTRS)

Grady, Joseph E.

2015-01-01

The Non-Metallic Gas Turbine Engine project, funded by NASA Aeronautics Research Institute, represents the first comprehensive evaluation of emerging materials and manufacturing technologies that will enable fully nonmetallic gas turbine engines. This will be achieved by assessing the feasibility of using additive manufacturing technologies to fabricate polymer matrix composite and ceramic matrix composite turbine engine components. The benefits include: 50 weight reduction compared to metallic parts, reduced manufacturing costs, reduced part count and rapid design iterations. Two high payoff metallic components have been identified for replacement with PMCs and will be fabricated using fused deposition modeling (FDM) with high temperature polymer filaments. The CMC effort uses a binder jet process to fabricate silicon carbide test coupons and demonstration articles. Microstructural analysis and mechanical testing will be conducted on the PMC and CMC materials. System studies will assess the benefits of fully nonmetallic gas turbine engine in terms of fuel burn, emissions, reduction of part count, and cost. The research project includes a multidisciplinary, multiorganization NASA - industry team that includes experts in ceramic materials and CMCs, polymers and PMCs, structural engineering, additive manufacturing, engine design and analysis, and system analysis.

JOINING DISSIMILAR MATERIALS USING FRICTION STIR SCRIBE TECHNIQUE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Upadhyay, Piyush; Hovanski, Yuri; Jana, Saumyadeep

2016-09-01

Development of robust and cost effective method of joining dissimilar materials can provide a critical pathway to enable widespread use of multi-material design and components in mainstream industrial applications. The use of multi-material components such as Steel-Aluminum, Aluminum-Polymer allows design engineers to optimize material utilization based on service requirements and often lead weight and cost reductions. However producing an effective joint between materials with vastly different thermal, microstructural and deformation response is highly problematic using conventional joining and /or fastening methods. This is especially challenging in cost sensitive high volume markets that largely rely on low–cost joining solutions. Friction Stirmore » Scribe technology was developed to meet the demands of joining materials with drastically different properties and melting regimes. The process enables joining of light metals like Magnesium and Aluminum to high temperature materials like Steels and Titanium. Additionally viable joints between polymer composites and metal can also be made using this method. This paper will present state of the art, progress made and challenges associated with this innovative derivative of Friction Stir welding in reference to joining dissimilar metals and polymer/metal combinations.« less

Joining Dissimilar Materials Using Friction Stir Scribe Technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Upadhyay, Piyush; Hovanski, Yuri; Jana, Saumyadeep

2016-10-03

Development of a robust and cost-effective method of joining dissimilar materials could provide a critical pathway to enable widespread use of multi-material designs and components in mainstream industrial applications. The use of multi-material components such as steel-aluminum and aluminum-polymer would allow design engineers to optimize material utilization based on service requirements and could often lead to weight and cost reductions. However, producing an effective joint between materials with vastly different thermal, microstructural, and deformation responses is highly problematic using conventional joining and/or fastening methods. This is especially challenging in cost sensitive, high volume markets that largely rely on low costmore » joining solutions. Friction stir scribe technology was developed to meet the demands of joining materials with drastically different properties and melting regimes. The process enables joining of light metals like magnesium and aluminum to high temperature materials like steel and titanium. Viable joints between polymer composites and metal can also be made using this method. This paper will present the state of the art, progress made, and challenges associated with this innovative derivative of friction stir welding in reference to joining dissimilar metals and polymer/metal combinations.« less

Direct micropatterning of polymer materials by ice mold

NASA Astrophysics Data System (ADS)

Yu, Xinhong; Xing, Rubo; Luan, Shifang; Wang, Zhe; Han, Yanchun

2006-10-01

Micropatterning of functional polymer materials by micromolding in capillaries (MIMIC) with ice mold is reported in this paper. Ice mold was selected due to its thaw or sublimation. Thus, the mold can be easily removed. Furthermore, the polymer solution did not react with, swell, or adhere to the ice mold, so the method is suitable for many kinds of materials (such as P3HT, PMMA Alq 3/PVK, PEDOT: PSS, PS, P2VP, etc.). Freestanding polymer microstructures, binary polymer pattern, and microchannels have been fabricated by the use of ice mold freely.

Spectroscopic studies of PVA/Gly:Na2SO4 polymer composites

NASA Astrophysics Data System (ADS)

G, Thejas Urs; T, Ananda H.; Mahadevaiah, Somashekar, R.

2015-06-01

As a continued work on investigating a good conducting polymer, Sodium sulphate doped PVA polymer composites were prepared by solution casting method and subjected to various analytical measurements such as FT-IR spectroscopy, UV/Visible absorbance and Wide angle X-ray scattering technique. The changes observed in the structure of these polymer composites for various concentrations are computed by the results obtained from all above techniques are reported and related with the structure property. The Microstructural parameters of these polymer composites are evaluated using in-house programs.

Tunable Infrared Metasurface on a Soft Polymer Scaffold.

PubMed

Reeves, Jeremy B; Jayne, Rachael K; Stark, Thomas J; Barrett, Lawrence K; White, Alice E; Bishop, David J

2018-05-09

The fabrication of metallic electromagnetic meta-atoms on a soft microstructured polymer scaffold using a MEMS-based stencil lithography technique is demonstrated. Using this technique, complex metasurfaces that are generally impossible to fabricate with traditional photolithographic techniques are created. By engineering the mechanical deformation of the polymer scaffold, the metasurface reflectivity in the mid-infrared can be tuned by the application of moderate strains.

Southern Regional Center for Lightweight Innovative Design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horstemeyer, Mark F.; Wang, Paul

The three major objectives of this Phase III project are: To develop experimentally validated cradle-to-grave modeling and simulation tools to optimize automotive and truck components for lightweighting materials (aluminum, steel, and Mg alloys and polymer-based composites) with consideration of uncertainty to decrease weight and cost, yet increase the performance and safety in impact scenarios; To develop multiscale computational models that quantify microstructure-property relations by evaluating various length scales, from the atomic through component levels, for each step of the manufacturing process for vehicles; and To develop an integrated K-12 educational program to educate students on lightweighting designs and impact scenarios.

Hydroxyapatite scaffolds processed using a TBA-based freeze-gel casting/polymer sponge technique.

PubMed

Yang, Tae Young; Lee, Jung Min; Yoon, Seog Young; Park, Hong Chae

2010-05-01

A novel freeze-gel casting/polymer sponge technique has been introduced to fabricate porous hydroxyapatite scaffolds with controlled "designer" pore structures and improved compressive strength for bone tissue engineering applications. Tertiary-butyl alcohol (TBA) was used as a solvent in this work. The merits of each production process, freeze casting, gel casting, and polymer sponge route were characterized by the sintered microstructure and mechanical strength. A reticulated structure with large pore size of 180-360 microm, which formed on burn-out of polyurethane foam, consisted of the strut with highly interconnected, unidirectional, long pore channels (approximately 4.5 microm in dia.) by evaporation of frozen TBA produced in freeze casting together with the dense inner walls with a few, isolated fine pores (<2 microm) by gel casting. The sintered porosity and pore size generally behaved in an opposite manner to the solid loading, i.e., a high solid loading gave low porosity and small pore size, and a thickening of the strut cross section, thus leading to higher compressive strengths.

Modeling out-of-plane actuation in thin-film nematic polymer networks: From chiral ribbons to auto-origami boxes via twist and topology

PubMed Central

Gimenez-Pinto, Vianney; Ye, Fangfu; Mbanga, Badel; Selinger, Jonathan V.; Selinger, Robin L. B.

2017-01-01

Various experimental and theoretical studies demonstrate that complex stimulus-responsive out-of-plane distortions such as twist of different chirality, emergence of cones, simple and anticlastic bending can be engineered and pre-programmed in a liquid crystalline rubbery material given a well-controlled director microstructure. Via 3-d finite element simulation studies, we demonstrate director-encoded chiral shape actuation in thin-film nematic polymer networks under external stimulus. Furthermore, we design two complex director fields with twisted nematic domains and nematic disclinations that encode a pattern of folds for an auto-origami box. This actuator will be flat at a reference nematic state and form four well-controlled bend distortions as orientational order changes. Device fabrication is applicable via current experimental techniques. These results are in qualitative agreement with theoretical predictions, provide insight into experimental observations, and demonstrate the value of finite element methods at the continuum level for designing and engineering liquid crystal polymeric devices. PMID:28349949

Evolution of the microstructure of unmodified and polymer modified asphalt binders with aging in an accelerated weathering tester.

PubMed

Menapace, Ilaria; Masad, Eyad

2016-09-01

This paper presents findings on the evolution of the surface microstructure of two asphalt binders, one unmodified and one polymer modified, directly exposed to aging agents with increasing durations. The aging is performed using an accelerated weathering tester, where ultraviolet radiation, oxygen and an increased temperature are applied to the asphalt binder surface. Ultraviolet and dark cycles, which simulated the succession of day and night, alternated during the aging process, and also the temperature varied, which corresponded to typical summer day and night temperatures registered in the state of Qatar. Direct aging of an exposed binder surface is more effective in showing microstructural modifications than previously applied protocols, which involved the heat treatment of binders previously aged with standardized methods. With the new protocol, any molecular rearrangements in the binder surface after aging induced by the heat treatment is prevented. Optical photos show the rippling and degradation of the binder surface due to aging. Microstructure images obtained by means of atomic force microscopy show gradual alteration of the surface due to aging. The original relatively flat microstructure was substituted with a profoundly different microstructure, which significantly protrudes from the surface, and is characterized by various shapes, such as rods, round structures and finally 'flower' or 'leaf' structures. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.

First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

Improved construction materials for polar regions using microcellular thermoplastic foams

NASA Technical Reports Server (NTRS)

Cunningham, Daniel J.

1994-01-01

Microcellular polymer foams (MCF) are thermoplastic foams with very small cell diameters, less than 10 microns, and very large cell densities, 10(exp 9) to 10(exp 15) cells per cubic centimeter of unfoamed material. The concept of foaming polymers with microcellular voids was conceived to reduce the amount of material used for mass-produced items without compromising the mechanical properties. The reasoning behind this concept was that if voids smaller than the critical flaw size pre-existing in polymers were introduced into the matrix, they would not affect the overall strength of the product. MCF polycarbonate (PC), polystyrene (PS), and polyvinyl chloride (PVC) were examined to determine the effects of the microstructure towards the mechanical properties of the materials at room and arctic temperatures. Batch process parameters were discovered for these materials and foamed samples of three densities were produced for each material. To quantify the toughness and strength of these polymers, the tensile yield strength, tensile toughness, and impact resistance were measured at room and arctic temperatures. The feasibility of MCF polymers has been demonstrated by the consistent and repeatable MCF microstructures formed, but the improvements in the mechanical properties were not conclusive. Therefore the usefulness of the MCF polymers to replace other materials in arctic environments is questionable.

An e.s.c.a. study of atomic oxygen interactions with phosphazene-coated polyimide films

NASA Technical Reports Server (NTRS)

Fewell, Larry L.; Finney, Lorie

1991-01-01

Metallic as well as most nonmetallic materials experience oxidation and mass loss via surface erosion in low earth orbit as shown in previous Space Shuttle flights. This study is an evaluation of select polyphosphazene polymers and their resistance to atomic oxygen attack. Electron spectroscopy for chemical analysis examinations of the surfaces of polyphosphazene coatings were monitored for microstructural changes induced during exposures to atomic oxygen. Sample exposures in oxygen plasmas and O(3P) beam were compared as to their effect on surface compositional changes in the polyphosphazene coating. High resolution line scans revealed rearrangements in the polymer backbone and scissioning reactions involving fluorocarbon units of long chain fluoroalkoxy pendant groups. Atom percents and peak areas of all species provided a detailed profile of the microstructural changes induced in phosphazene polymers as a result of exposures to atomic oxygen.

Recent Developments in Ultra High Temperature Ceramics at NASA Ames

NASA Technical Reports Server (NTRS)

Johnson, Sylvia M.; Gasch, Matt; Lawson, John W.; Gusman, Michael I.; Stackpole, Margaret M.

2009-01-01

NASA Ames is pursuing a variety of approaches to modify and control the microstructure of UHTCs with the goal of improving fracture toughness, oxidation resistance and controlling thermal conductivity. The overall goal is to produce materials that can perform reliably as sharp leading edges or nose tips in hypersonic reentry vehicles. Processing approaches include the use of preceramic polymers as the SiC source (as opposed to powder techniques), the addition of third phases to control grain growth and oxidation, and the use of processing techniques to produce high purity materials. Both hot pressing and field assisted sintering have been used to make UHTCs. Characterization of the mechanical and thermal properties of these materials is ongoing, as is arcjet testing to evaluate performance under simulated reentry conditions. The preceramic polymer approach has generated a microstructure in which elongated SiC grains grow in the form of an in-situ composite. This microstructure has the advantage of improving fracture toughness while potentially improving oxidation resistance by reducing the amount and interconnectivity of SiC in the material. Addition of third phases, such as Ir, results in a very fine-grained microstructure, even in hot-pressed samples. The results of processing and compositional changes on microstructure and properties are reported, along with selected arcjet results.

Effect of Polymer Matrix on the Structure and Electric Properties of Piezoelectric Lead Zirconatetitanate/Polymer Composites

PubMed Central

Li, Rui; Zhou, Jun; Liu, Hujun; Pei, Jianzhong

2017-01-01

Piezoelectric lead zirconatetitanate (PZT)/polymer composites were prepared by two typical polymer matrixes using the hot-press method. The micromorphology, microstructure, dielectric properties, and piezoelectric properties of the PZT/polymer composites were characterized and investigated. The results showed that when the condition of frequency is 103 Hz, the dielectric and piezoelectric properties of PZT/poly(vinylidene fluoride) were both better than that of PZT/polyvinyl chloride (PVC). When the volume fraction of PZT was 50%, PZT/PVDF prepared by the hot-press method had better comprehensive electric property. PMID:28805730

Melem-based derivatives as metal-free photocatalysts for simultaneous reduction of Cr(VI) and degradation of 5-Sulfosalicylic acid.

PubMed

Lan, Huachun; Li, Lili; Liu, Huijuan; An, Xiaoqiang; Liu, Fei; Chen, Cuibai; Qu, Jiuhui

2017-12-01

Carbon nitride has been considered as promising metal-free polymers for low-cost photocatalysis. Most prevailing concern about this fantastic material focuses on g-C 3 N 4 , while the potential of other derivatives have been overlooked. Herein, in order to determine the desired derivatives for environmental pollutant treatment, the impact of degree of thermal polymerization on the microstructure of carbon nitride was investigated. Interestingly, melem-based derivatives exhibit 4- and 6-fold enhanced activities than g-C 3 N 4 , when used as synergetic photocatalysts for the simultaneous treatment of heavy metal ions and organic contaminants. According to the fundamental study of reactive species formation, a microstructure-dependent photocatalytic mechanism was established. Hydrogen bond-facilitated trapping of photogenerated holes and superior ability for oxygen molecular activation contributed to the high-performance of melem-based derivatives. In contrast, g-C 3 N 4 shows inferior performance during superoxide radical-dominated photodegradation reactions, as its microstructure is favorable for the generation of . Our research not only sheds new insights into the microstructure design of metal-free carbon nitride photocatalysts, but also has immense scientific and technological values for high-efficiency and synergetic environmental applications. Copyright © 2017 Elsevier Inc. All rights reserved.

Fabrication of a biomimetic elastic intervertebral disk scaffold using additive manufacturing.

PubMed

Whatley, Benjamin R; Kuo, Jonathan; Shuai, Cijun; Damon, Brooke J; Wen, Xuejun

2011-03-01

A custom-designed three-dimensional additive manufacturing device was developed to fabricate scaffolds for intervertebral disk (IVD) regeneration. This technique integrated a computer with a device capable of 3D movement allowing for precise motion and control over the polymer scaffold resolution. IVD scaffold structures were designed using computer-aided design to resemble the natural IVD structure. Degradable polyurethane (PU) was used as an elastic scaffold construct to mimic the elastic nature of the native IVD tissue and was deposited at a controlled rate using ultra-fine micropipettes connected to a syringe pump. The elastic PU was extruded directly onto a collecting substrate placed on a freezing stage. The three-dimensional movement of the computer-controlled device combined with the freezing stage enabled precise control of polymer deposition using extrusion. The addition of the freezing stage increased the polymer solution viscosity and hardened the polymer solution as it was extruded out of the micropipette tip. This technique created scaffolds with excellent control over macro- and micro-structure to influence cell behavior, specifically for cell adhesion, proliferation, and alignment. Concentric lamellae were printed at a high resolution to mimic the native shape and structure of the IVD. Seeded cells aligned along the concentric lamellae and acquired cell morphology similar to native tissue in the outer portion of the IVD. The fabricated scaffolds exhibited elastic behavior during compressive and shear testing, proving that the scaffolds could support loads with proper fatigue resistance without permanent deformation. Additionally, the mechanical properties of the scaffolds were comparable to those of native IVD tissue.

Polymer/silica hybrid waveguide temperature sensor based on asymmetric Mach-Zehnder interferometer

NASA Astrophysics Data System (ADS)

Niu, Donghai; Wang, Xibin; Sun, Shiqi; Jiang, Minghui; Xu, Qiang; Wang, Fei; Wu, Yuanda; Zhang, Daming

2018-04-01

A highly sensitive waveguide temperature sensor based on asymmetric Mach-Zehnder interferometer was designed and experimentally demonstrated. The interferometer is based on the polymer/silica hybrid waveguide structure, and Norland Optical Adhesive 73 (NOA 73) was employed as the waveguide core to enhance the temperature sensitivity. The influence of the different length differences between the two interferometer arms on the sensitivity of the sensor was systemically studied. It is shown that the maximum temperature sensitivity of -431 pm °C-1 can be obtained in the range of 25 °C-75 °C, while the length difference is 92 μm. Moreover, the temperature sensitivity contributions from different core materials were also investigated experimentally. It is shown that the waveguide material and microstructure of the device have significant influences on the sensitivity of the waveguide temperature sensor.

Nonlinear oscillatory rheology and structure of wormlike micellar solutions and colloidal suspensions

NASA Astrophysics Data System (ADS)

Gurnon, Amanda Kate

The complex, nonlinear flow behavior of soft materials transcends industrial applications, smart material design and non-equilibrium thermodynamics. A long-standing, fundamental challenge in soft-matter science is establishing a quantitative connection between the deformation field, local microstructure and macroscopic dynamic flow properties i.e., the rheology. Soft materials are widely used in consumer products and industrial processes including energy recovery, surfactants for personal healthcare (e.g. soap and shampoo), coatings, plastics, drug delivery, medical devices and therapeutics. Oftentimes, these materials are processed by, used during, or exposed to non-equilibrium conditions for which the transient response of the complex fluid is critical. As such, designing new dynamic experiments is imperative to testing these materials and further developing micromechanical models to predict their transient response. Two of the most common classes of these soft materials stand as the focus of the present research; they are: solutions of polymer-like micelles (PLM or also known as wormlike micelles, WLM) and concentrated colloidal suspensions. In addition to their varied applications these two different classes of soft materials are also governed by different physics. In contrast, to the shear thinning behavior of the WLMs at high shear rates, the near hard-sphere colloidal suspensions are known to display increases, sometimes quite substantial, in viscosity (known as shear thickening). The stress response of these complex fluids derive from the shear-induced microstructure, thus measurements of the microstructure under flow are critical for understanding the mechanisms underlying the complex, nonlinear rheology of these complex fluids. A popular micromechanical model is reframed from its original derivation for predicting steady shear rheology of polymers and WLMs to be applicable to weakly nonlinear oscillatory shear flow. The validity, utility and limits of this constitutive model are tested by comparison with experiments on model WLM solutions. Further comparisons to the nonlinear oscillatory shear responses measured from colloidal suspensions establishes this analysis as a promising, quantitative method for understanding the underlying mechanisms responsible for the nonlinear dynamic response of complex fluids. A new experimental technique is developed to measure the microstructure of complex fluids during steady and transient shear flow using small-angle neutron scattering (SANS). The Flow-SANS experimental method is now available to the broader user communities at the NIST Center for Neutron Research, Gaithersburg, MD and the Institut Laue-Langevin, Grenoble, France. Using this new method, a model shear banding WLM solution is interrogated under steady and oscillatory shear. For the first time, the flow-SANS methods identify new metastable states for shear banding WLM solutions, thus establishing the method as capable of probing new states not accessible using traditional steady or linear oscillatory shear methods. The flow-induced three-dimensional microstructure of a colloidal suspension under steady and dynamic oscillatory shear is also measured using these rheo- and flow-SANS methods. A new structure state is identified in the shear thickening regime that proves critical for defining the "hydrocluster" microstructure state of the suspension that is responsible for shear thickening. For both the suspensions and the WLM solutions, stress-SANS rules with the measured microstructures define the individual stress components arising separately from conservative and hydrodynamic forces and these are compared with the macroscopic rheology. Analysis of these results defines the crucial length- and time-scales of the transient microstructure response. The novel dynamic microstructural measurements presented in this dissertation provide new insights into the complexities of shear thickening and shear banding flow phenomena, which are effects observed more broadly across many different types of soft materials. Consequently, the microstructure-rheology property relationships developed for these two classes of complex fluids will aid in the testing and advancement of micromechanical constitutive model development, smart material design, industrial processing and fundamental non-equilibrium thermodynamic research of a broad range of soft materials.

One-Pot Synthesis of Multifunctional Polymers by Light-Controlled Radical Polymerization and Enzymatic Catalysis with Candida antarctica Lipase B.

PubMed

Hrsic, Emin; Keul, Helmut; Möller, Martin

2015-12-01

The preparation of multifunctional polymers and block copolymers by a straightforward one-pot reaction process that combines enzymatic transacylation with light-controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light-controlled polymerization, leading to multifunctional methacrylate-based polymers with well-defined microstructure. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cellulose Nanocrystals vs. Cellulose Nanofibrils: A Comparative study on Their Microstructures and Effects as Polymer Reinforcing Agents

Treesearch

Xuezhu Xu; Fei Liu; Long Jiang; J.Y. Zhu; Darrin Haagenson; Dennis P. Wiesenborn

2013-01-01

Both cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are nanoscale cellulose fibers that have shown reinforcing effects in polymer nanocomposites. CNCs and CNFs are different in shape, size and composition. This study systematically compared their morphologies, crystalline structure, dispersion properties in polyethylene oxide (PEO) matrix, interactions...

In-situ 3D visualization of composite microstructure during polymer-to-ceramic conversion

DOE PAGES

Larson, Natalie M.; Zok, Frank W.

2017-10-31

One route for producing fiber-reinforced ceramic-matrix composites entails repeated impregnation and pyrolysis of a preceramic polymer in a fiber preform. The process relies crucially on the development of networks of contiguous cracks during pyrolysis, thereby allowing further impregnation to attain nearly-full densification. The present study employs in-situ x-ray computed tomography (XCT) to reveal in three dimensions the evolution of matrix structure during pyrolysis of a SiC-based preceramic polymer to 1200 °C. Observations are used to guide the development of a taxonomy of crack geometries and crack structures and to identify the temporal sequence of their formation. A quantitative analysis ismore » employed to characterize effects of local microstructural dimensions on the conditions required to form cracks of various types. Complementary measurements of gas evolution and mass loss of the preceramic polymer during pyrolysis as well as changes in mass density and Young's modulus provide context for the physical changes revealed by XCT. Furthermore, the findings provide a foundation for future development of physics-based models to guide composite fabrication processes.« less

Measurement of the trapping and detrapping properties of polymers in relation with their microstructure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vallayer, B.; Hourquebie, P.; Marsacq, D.

1996-12-31

In the field of Space Charge Physics, the role of electrical traps on space charge behavior and therefore on the breakdown properties has been now well-established. However, the traps in polymers are very difficult to define compared to the case of ceramics for which a lot of studies have been performed. A new specific method for measuring the trapping and detrapping properties of dielectric materials has been developed. This method allows to characterize the electrostatic state of an insulating sample after irradiation by a high energy electron beam. The authors discuss the basis of the method and its general possibilitiesmore » to measure the breakdown relevant parameters as the secondary electron yield for instance. Moreover, the method has been used on several polymers as HDPE and LDPE. The difference of trapping properties between those materials can be explained by microstructure evolutions (crystallinity ratio) due to a difference of the branching rate. This difference of trapping and detrapping properties of these two polymers could be connected to the breakdown behavior of the two materials which is known to be very different.« less

2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion

NASA Astrophysics Data System (ADS)

Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

2016-08-01

Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

A Multiscale, Nonlinear, Modeling Framework Enabling the Design and Analysis of Composite Materials and Structures

NASA Technical Reports Server (NTRS)

Bednarcyk, Brett A.; Arnold, Steven M.

2012-01-01

A framework for the multiscale design and analysis of composite materials and structures is presented. The ImMAC software suite, developed at NASA Glenn Research Center, embeds efficient, nonlinear micromechanics capabilities within higher scale structural analysis methods such as finite element analysis. The result is an integrated, multiscale tool that relates global loading to the constituent scale, captures nonlinearities at this scale, and homogenizes local nonlinearities to predict their effects at the structural scale. Example applications of the multiscale framework are presented for the stochastic progressive failure of a SiC/Ti composite tensile specimen and the effects of microstructural variations on the nonlinear response of woven polymer matrix composites.

A Multiscale, Nonlinear, Modeling Framework Enabling the Design and Analysis of Composite Materials and Structures

NASA Technical Reports Server (NTRS)

Bednarcyk, Brett A.; Arnold, Steven M.

2011-01-01

A framework for the multiscale design and analysis of composite materials and structures is presented. The ImMAC software suite, developed at NASA Glenn Research Center, embeds efficient, nonlinear micromechanics capabilities within higher scale structural analysis methods such as finite element analysis. The result is an integrated, multiscale tool that relates global loading to the constituent scale, captures nonlinearities at this scale, and homogenizes local nonlinearities to predict their effects at the structural scale. Example applications of the multiscale framework are presented for the stochastic progressive failure of a SiC/Ti composite tensile specimen and the effects of microstructural variations on the nonlinear response of woven polymer matrix composites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Tianyu; Xu, Hongyi; Chen, Wei

Fiber-reinforced polymer composites are strong candidates for structural materials to replace steel and light alloys in lightweight vehicle design because of their low density and relatively high strength. In the integrated computational materials engineering (ICME) development of carbon fiber composites, microstructure reconstruction algorithms are needed to generate material microstructure representative volume element (RVE) based on the material processing information. The microstructure RVE reconstruction enables the material property prediction by finite element analysis (FEA)This paper presents an algorithm to reconstruct the microstructure of a chopped carbon fiber/epoxy laminate material system produced by compression molding, normally known as sheet molding compounds (SMC).more » The algorithm takes the result from material’s manufacturing process as inputs, such as the orientation tensor of fibers, the chopped fiber sheet geometry, and the fiber volume fraction. The chopped fiber sheets are treated as deformable rectangle chips and a random packing algorithm is developed to pack these chips into a square plate. The RVE is built in a layer-by-layer fashion until the desired number of lamina is reached, then a fine tuning process is applied to finalize the reconstruction. Compared to the previous methods, this new approach has the ability to model bended fibers by allowing limited amount of overlaps of rectangle chips. Furthermore, the method does not need SMC microstructure images, for which the image-based characterization techniques have not been mature enough, as inputs. Case studies are performed and the results show that the statistics of the reconstructed microstructures generated by the algorithm matches well with the target input parameters from processing.« less

Dielectric Characteristics of Microstructural Changes and Property Evolution in Engineered Materials

NASA Astrophysics Data System (ADS)

Clifford, Jallisa Janet

Heterogeneous materials are increasingly used in a wide range of applications such as aerospace, civil infrastructure, fuel cells and many others. The ability to take properties from two or more materials to create a material with properties engineered to needs is always very attractive. Hence heterogeneous materials are evolving into more complex formulations in multiple disciplines. Design of microstructure at multiple scales control the global functional properties of these materials and their structures. However, local microstructural changes do not directly cause a proportional change to the global properties (such as strength and stiffness). Instead, local changes follow an evolution process including significant interactions. Therefore, in order to understand property evolution of engineered materials, microstructural changes need to be effectively captured. Characterizing these changes and representing them by material variables will enable us to further improve our material level understanding. In this work, we will demonstrate how microstructural features of heterogeneous materials can be described quantitatively using broadband dielectric spectroscopy (BbDS). The frequency dependent dielectric properties can capture the change in material microstructure and represent these changes in terms of material variables, such as complex permittivity. These changes in terms of material properties can then be linked to a number of different conditions, such as increasing damage due to impact or fatigue. Two different broadband dielectric spectroscopy scanning modes are presented: bulk measurements and continuous scanning to measure dielectric property change as a function of position across the specimen. In this study, we will focus on ceramic materials and fiber reinforced polymer matrix composites as test bed material systems. In the first part of the thesis, we will present how different micro-structural design of porous ceramic materials can be captured quantitatively using BbDS. These materials are typically used in solid oxide fuel cells (SOFC). Results show significant effect of microstructural design on material properties at multiple temperatures (up to 800 °C). In the later part of the thesis, we will focus on microstructural changes of fiber reinforced composite materials due to impact and static loading. The changes in dielectric response can then be linked to the bulk mechanical properties of the material and various damage modes. Observing trends in dielectric response enables us to further determine local mechanisms and distribution of properties throughout the damaged specimens. A 3D X-ray microscope and a digital microscope have been used to visualize these changes in material microstructure and validate experimental observations. The increase in damage observed in the material microstructure can then also be linked to the changes in dielectric response. Results show that BbDS is an extremely useful tool for identifying microstructural changes within a heterogeneous material and particularly useful in relating remaining properties. Dielectric material variables can be used directly in property degradation laws and help develop a framework for future predictive modeling methodologies.

Scattering from Colloid-Polymer Conjugates with Excluded Volume Effect

DOE PAGES

Li, Xin; Sanchez-Diaz, Luis E.; Smith, Gregory Scott; ...

2015-01-13

This work presents scattering functions of conjugates consisting of a colloid particle and a self-avoiding polymer chain as a model for protein-polymer conjugates and nanoparticle-polymer conjugates in solution. The model is directly derived from the two-point correlation function with the inclusion of excluded volume effects. The dependence of the calculated scattering function on the geometric shape of the colloid and polymer stiffness is investigated. The model is able to describe the experimental scattering signature of the solutions of suspending hard particle-polymer conjugates and provide additional conformational information. This model explicitly elucidates the link between the global conformation of a conjugatemore » and the microstructure of its constituent components.« less

The effect of silica toward polymer membrane for water separation process

NASA Astrophysics Data System (ADS)

Jamalludin, Mohd Riduan; Rosli, M. U.; Ishak, Muhammad Ikman; Khor, C. Y.; Shahrin, Suhaimi; Ismail, Ras Izzati; Lailina N., M.; Leng Y., L.; Jahidi, H.

2017-09-01

The aim of this present work was to investigate the effect of different percentage rice husk silica (RHS) particles composition towards polymer mixed matrix membrane microstructure and performance in water separation process. The polymer membranes were prepared by a phase inversion method using polysulfone (PSf), N-methyl-2-pyrrolidone (NMP) as solvent, distilled water as non-solvent and fixed RHS at 400°C as an additive. The microstructures of PSf/PEG/RHS sample were characterized by performing scanning electron microscope (SEM). The performance was measured by using pure water flux and humic acid for the rejection test. The analyzed result of SEM analysis revealed that the addition of RHS obviously improved the microstructure of the membrane especially at the top and sub layer at the range of 1 until 3 wt. %. This was proven by the pure water flux (PWF) value measured from 114.47 LMH to 154.04 LMH and rejection from value 83% to 96% at this specified range substantially higher than the mixed matrix membrane with synthetic silica. In fact, the presence of RHS particles not only improved the properties and performance of membrane but also possess biodegradable properties which can minimize the pollution and provide a membrane green technology system.

International Conference on Electronic Processes in Organic Materials (6th) Held in Gurzuf, Crimea, Ukraine, on September 25-29, 2006

DTIC Science & Technology

2006-09-29

MEH-PPV and blends MEH-PPV/fullerene derivative to investigate the charge transfer process . Microstructure - properties correlation of blends polymer...liquid crystals 4. Nonlinear properties of organic structures and composites 5. Electronic processes within polymer composites 6. Nanostructures. Polymer...P.A.Kondratenko, Yu.M.Lopatkin, TN.Sakun. SPECTROSCOPIC PROPERTIES AND PROCESSES OF PHOTODISSOCIATION OF DYES ....... 32 D.-Q. Feng, D. Wisbey, Y. Ta4 Ya. B

Fabrication of mesoporous polymer monolith: a template-free approach.

PubMed

Okada, Keisuke; Nandi, Mahasweta; Maruyama, Jun; Oka, Tatsuya; Tsujimoto, Takashi; Kondoh, Katsuyoshi; Uyama, Hiroshi

2011-07-14

Mesoporous polyacrylonitrile (PAN) monolith has been fabricated by a template-free approach using the unique affinity of PAN towards a water/dimethyl sulfoxide (DMSO) mixture. A newly developed Thermally Induced Phase Separation Technique (TIPS) has been used to obtain the polymer monoliths and their microstructures have been controlled by optimizing the concentration and cooling temperature.

Localized etching of polymer films using an atmospheric pressure air microplasma jet

NASA Astrophysics Data System (ADS)

Guo, Honglei; Liu, Jingquan; Yang, Bin; Chen, Xiang; Yang, Chunsheng

2015-01-01

A direct-write process device based on the atmospheric pressure air microplasma jet (AμPJ) has been developed for the localized etching of polymer films. The plasma was generated by the air discharge ejected out through a tip-nozzle (inner diameter of 100 μm), forming the microplasma jet. The AμPJ was capable of reacting with the polymer surface since it contains a high concentration of oxygen reactive species and thus resulted in the selective removal of polymer films. The experimental results demonstrated that the AμPJ could fabricate different microstructures on a parylene-C film without using any masks or causing any heat damage. The etch rate of parylene-C reached 5.1 μm min-1 and microstructures of different depth and width could also be realized by controlling two process parameters, namely, the etching time and the distance between the nozzle and the substrate. In addition, combining XPS analysis and oxygen-induced chemical etching principles, the potential etching mechanism of parylene-C by the AμPJ was investigated. Aside from the etching of parylene-C, micro-holes on the photoresist and polyimide film were successfully created by the AμPJ. In summary, maskless pattern etching of polymer films could be achieved using this AμPJ.

3-dimensional free standing micro-structures by proton beam writing of Su 8-silver nanoParticle polymeric composite

NASA Astrophysics Data System (ADS)

Igbenehi, H.; Jiguet, S.

2012-09-01

Proton beam lithography a maskless direct-write lithographic technique (well suited for producing 3-Dimensional microstructures in a range of resist and semiconductor materials) is demonstrated as an effective tool in the creation of electrically conductive freestanding micro-structures in an Su 8 + Nano Silver polymer composite. The structures produced show non-ohmic conductivity and fit the percolation theory conduction model of tunneling of separated nanoparticles. Measurements show threshold switching and a change in conductivity of at least 4 orders of magnitude. The predictable range of protons in materials at a given energy is exploited in the creation of high aspect ratio, free standing micro-structures, made from a commercially available SU8 Silver nano-composite (GMC3060 form Gersteltec Inc. a negative tone photo-epoxy with added metallic nano-particles(Silver)) to create films with enhanced electrical properties when exposed and cured. Nano-composite films are directly written on with a finely focused MeV accelerated Proton particle beam. The energy loss of the incident proton beams in the target polymer nano- composite film is concentrated at the end of its range, where damage occurs; changing the chemistry of the nano-composite film via an acid initiated polymerization - creating conduction paths. Changing the energy of the incident beams provide exposed regions with different penetration and damage depth - exploited in the demonstrated cantilever microstructure.

3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

NASA Astrophysics Data System (ADS)

Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; Worsley, Marcus A.; Wu, Amanda S.; Kanarska, Yuliya; Horn, John D.; Duoss, Eric B.; Ortega, Jason M.; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A.; King, Michael J.

2017-03-01

Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.

Learning from Natural Nacre: Constructing Layered Polymer Composites with High Thermal Conductivity.

PubMed

Pan, Guiran; Yao, Yimin; Zeng, Xiaoliang; Sun, Jiajia; Hu, Jiantao; Sun, Rong; Xu, Jian-Bin; Wong, Ching-Ping

2017-09-27

Inspired by the microstructures of naturally layered and highly oriented materials, such as natural nacre, we report a thermally conductive polymer composite that consists of epoxy resin and Al 2 O 3 platelets deposited with silver nanoparticles (AgNPs). Owing to their unique two-dimensional structure, Al 2 O 3 platelets are stacked together via a hot-pressing technique, resulting in a brick-and-mortar structure, which is similar to the one of natural nacre. Moreover, the AgNPs deposited on the surfaces of the Al 2 O 3 platelets act as bridges that link the adjacent Al 2 O 3 platelets due to the reduced melting point of the AgNPs. As a result, the polymer composite with 50 wt % filler achieves a maximum thermal conductivity of 6.71 W m -1 K -1 . In addition, the small addition of AgNPs (0.6 wt %) minimally affects the electrical insulation of the composites. Our bioinspired approach will find uses in the design and fabrication of thermally conductive materials for thermal management in modern electronics.

3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng

Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignmentmore » within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Moreover, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.« less

Taming Self-Organization Dynamics to Dramatically Control Porous Architectures.

PubMed

Daly, Ronan; Sader, John E; Boland, John J

2016-03-22

We demonstrate templating of functional materials with unexpected and intricate micro- and nanostructures by controlling the condensation, packing, and evaporation of water droplets on a polymer solution. Spontaneous evaporation of a polymer solution induces cooling of the liquid surface and water microdroplet condensation from the ambient vapor. These droplets pack together and act as a template to imprint an entangled polymer film. This breath figure (BF) phenomenon is an example of self-organization that involves the long-range ordering of droplets. Equilibrium-based analysis provides many insights into contact angles and drop stability of individual drops, but the BF phenomenon remains poorly understood thus far, preventing translation to real applications. Here we investigate the dynamics of this phenomenon to separate out the competing influences and then introduce a modulation scheme to ultimately manipulate the water vapor-liquid equilibrium independently from the solvent evaporation. This approach to BF control provides insights into the mechanism, a rationale for microstructure design, and evidence for the benefits of dynamical control of self-organization systems. We finally present dramatically different porous architectures from this approach reminiscent of microscale Petri dishes, conical flasks, and test tubes.

3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

DOE PAGES

Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; ...

2017-03-06

Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignmentmore » within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Moreover, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.« less

3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties.

PubMed

Lewicki, James P; Rodriguez, Jennifer N; Zhu, Cheng; Worsley, Marcus A; Wu, Amanda S; Kanarska, Yuliya; Horn, John D; Duoss, Eric B; Ortega, Jason M; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A; King, Michael J

2017-03-06

Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.

3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties

PubMed Central

Lewicki, James P.; Rodriguez, Jennifer N.; Zhu, Cheng; Worsley, Marcus A.; Wu, Amanda S.; Kanarska, Yuliya; Horn, John D.; Duoss, Eric B.; Ortega, Jason M.; Elmer, William; Hensleigh, Ryan; Fellini, Ryan A.; King, Michael J.

2017-01-01

Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response. PMID:28262669

Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide

NASA Astrophysics Data System (ADS)

Zhao, Xiaoli; Xu, Zhen; Zheng, Bingna; Gao, Chao

2013-11-01

Nacre realizes strength and toughness through hierarchical designs with primary ``brick and mortar'' structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0-100%), and proposed an equation to depict the relationship.

Quantitative structure-property relationship (QSPR) modeling of drug-loaded polymeric micelles via genetic function approximation.

PubMed

Wu, Wensheng; Zhang, Canyang; Lin, Wenjing; Chen, Quan; Guo, Xindong; Qian, Yu; Zhang, Lijuan

2015-01-01

Self-assembled nano-micelles of amphiphilic polymers represent a novel anticancer drug delivery system. However, their full clinical utilization remains challenging because the quantitative structure-property relationship (QSPR) between the polymer structure and the efficacy of micelles as a drug carrier is poorly understood. Here, we developed a series of QSPR models to account for the drug loading capacity of polymeric micelles using the genetic function approximation (GFA) algorithm. These models were further evaluated by internal and external validation and a Y-randomization test in terms of stability and generalization, yielding an optimization model that is applicable to an expanded materials regime. As confirmed by experimental data, the relationship between microstructure and drug loading capacity can be well-simulated, suggesting that our models are readily applicable to the quantitative evaluation of the drug-loading capacity of polymeric micelles. Our work may offer a pathway to the design of formulation experiments.

Quantitative Structure-Property Relationship (QSPR) Modeling of Drug-Loaded Polymeric Micelles via Genetic Function Approximation

PubMed Central

Lin, Wenjing; Chen, Quan; Guo, Xindong; Qian, Yu; Zhang, Lijuan

2015-01-01

Self-assembled nano-micelles of amphiphilic polymers represent a novel anticancer drug delivery system. However, their full clinical utilization remains challenging because the quantitative structure-property relationship (QSPR) between the polymer structure and the efficacy of micelles as a drug carrier is poorly understood. Here, we developed a series of QSPR models to account for the drug loading capacity of polymeric micelles using the genetic function approximation (GFA) algorithm. These models were further evaluated by internal and external validation and a Y-randomization test in terms of stability and generalization, yielding an optimization model that is applicable to an expanded materials regime. As confirmed by experimental data, the relationship between microstructure and drug loading capacity can be well-simulated, suggesting that our models are readily applicable to the quantitative evaluation of the drug-loading capacity of polymeric micelles. Our work may offer a pathway to the design of formulation experiments. PMID:25780923

Design and Concept of Polyzwitterionic Copolymer Microgel Drug Delivery Systems In Situ Loaded with Non-steroidal Anti-inflammatory Ibuprofen.

PubMed

Kostova, Bistra; Kamenska, Elena; Georgieva, Dilyana; Balashev, Konstantin; Rachev, Dimitar; Georgiev, George

2017-01-01

Nowadays, the modern pharmaceutical investigations are directed toward obtaining of new polymer micro- and nano-sized drug delivery carriers. In this respect, the use of hydrogel carriers based on polyzwitterions (PZIs) is an opportunity in the preparation of polymer drug delivery systems with desired characteristics. This paper describes the synthesis and characterization of micro-structured p(VA-co-DMAPS) systems with different compositions in situ loaded with Ibuprofen by emulsifier-free emulsion copolymerization (EEC) in water. The mean size of the prepared microparticles was measured by SEM and particles have been visualized by AFM. The inclusion of Ibuprofen in the polyzwitterionic copolymer microgel systems was established by using DSC. In vitro drug release experiments were carried out in order to estimate the ability of the obtained microgels to modify the release of water-insoluble Ibuprofen.

Percolated microstructures for multi-modal transport enhancement in porous active materials

DOEpatents

McKay, Ian Salmon; Yang, Sungwoo; Wang, Evelyn N.; Kim, Hyunho

2018-03-13

A method of forming a composite material for use in multi-modal transport includes providing three-dimensional graphene having hollow channels, enabling a polymer to wick into the hollow channels of the three-dimensional graphene, curing the polymer to form a cured three-dimensional graphene, adding an active material to the cured three-dimensional graphene to form a composite material, and removing the polymer from within the hollow channels. A composite material formed according to the method is also provided.

[The action of high-molecular linear polymers on the circulatory system].

PubMed

Grigorian, S S; Sokolova, I A; Shakhnazarov, A A

1995-01-01

An analysis of the hemodynamic consequences of the injections of long linear polymers with high molecular weight is introduced. These injections lead to an increase of the cardiac output, to a decrease of the blood pressure, and hence cause a reduction of the resistance to blood flow. It follows that such kind of polymers is able to normalize hemodynamics under some pathophysiological conditions, e.g., during experimental atherosclerosis, ischemic state, hemorrhagic shock. An addition of drag-reducing polymers into the blood system is associated with a modification of the blood flow microstructure itself.

Data characterizing tensile behavior of cenosphere/HDPE syntactic foam.

PubMed

Kumar, B R Bharath; Doddamani, Mrityunjay; Zeltmann, Steven E; Gupta, Nikhil; Ramakrishna, Seeram

2016-03-01

The data set presented is related to the tensile behavior of cenosphere reinforced high density polyethylene syntactic foam composites "Processing of cenosphere/HDPE syntactic foams using an industrial scale polymer injection molding machine" (Bharath et al., 2016) [1]. The focus of the work is on determining the feasibility of using an industrial scale polymer injection molding (PIM) machine for fabricating syntactic foams. The fabricated syntactic foams are investigated for microstructure and tensile properties. The data presented in this article is related to optimization of the PIM process for syntactic foam manufacture, equations and procedures to develop theoretical estimates for properties of cenospheres, and microstructure of syntactic foams before and after failure. Included dataset contains values obtained from the theoretical model.

Self-Assembled Tea Tannin Graft Copolymer as Nanocarriers for Antimicrobial Drug Delivery and Wound Healing Activity.

PubMed

Mahata, Denial; Nag, Ahindra; Nando, Golok B; Mandal, Santi M; Franco, Octavio L

2018-04-01

Green chemistry polymers from renewable resources have recently received much more attention from pharmaceutical researchers. However, the appropriate application of a polymer depends on its chemical nature, biocompatibility and microstructure. Here, tannin polyphenols from the common beverage, tea, are used to develop a novel self-assembled porous capsule as a microstructure of hydrogel for versatile biological applications, such as drug delivery, antioxidant and wound healing activity. Hydrogel has been successfully used for the delivery of both anticancer and antimicrobial drugs. The developed material shows excellent biocompatibility and antioxidant activity in vitro. The scratch assay for in vitro wound healing activity reveals their higher potential to repair the damaged cells in comparison to control.

Data characterizing tensile behavior of cenosphere/HDPE syntactic foam

PubMed Central

Kumar, B.R. Bharath; Doddamani, Mrityunjay; Zeltmann, Steven E.; Gupta, Nikhil; Ramakrishna, Seeram

2016-01-01

The data set presented is related to the tensile behavior of cenosphere reinforced high density polyethylene syntactic foam composites “Processing of cenosphere/HDPE syntactic foams using an industrial scale polymer injection molding machine” (Bharath et al., 2016) [1]. The focus of the work is on determining the feasibility of using an industrial scale polymer injection molding (PIM) machine for fabricating syntactic foams. The fabricated syntactic foams are investigated for microstructure and tensile properties. The data presented in this article is related to optimization of the PIM process for syntactic foam manufacture, equations and procedures to develop theoretical estimates for properties of cenospheres, and microstructure of syntactic foams before and after failure. Included dataset contains values obtained from the theoretical model. PMID:26937472

Dispersion-engineered and highly nonlinear microstructured polymer optical fibres

NASA Astrophysics Data System (ADS)

Frosz, Michael H.; Nielsen, Kristian; Hlubina, Petr; Stefani, Alessio; Bang, Ole

2009-05-01

We demonstrate dispersion-engineering of microstructured polymer optical fibres (mPOFs) made of poly(methyl methacrylate) (PMMA). A significant shift of the total dispersion from the material dispersion is confirmed through measurement of the mPOF dispersion using white-light spectral interferometry. The influence of strong loss peaks on the dispersion (through the Kramers-Kronig relations) is investigated theoretically. It is found that the strong loss peaks of PMMA above 1100 nm can significantly modify the dispersion, while the losses below 1100 nm only modify the dispersion slightly. To increase the nonlinearity of the mPOFs we investigated doping of PMMA with the highly-nonlinear dye Disperse Red 1. Both doping of a PMMA cane and direct doping of a PMMA mPOF was performed.

Deep X-ray lithography for the fabrication of microstructures at ELSA

NASA Astrophysics Data System (ADS)

Pantenburg, F. J.; Mohr, J.

2001-07-01

Two beamlines at the Electron Stretcher Accelerator (ELSA) of Bonn University are dedicated for the production of microstructures by deep X-ray lithography with synchrotron radiation. They are equipped with state-of-the-art X-ray scanners, maintained and used by Forschungszentrum Karlsruhe. Polymer microstructure heights between 30 and 3000 μm are manufactured regularly for research and industrial projects. This requires different characteristic energies. Therefore, ELSA operates routinely at 1.6, 2.3 and 2.7 GeV, for high-resolution X-ray mask fabrication, deep and ultra-deep X-ray lithography, respectively. The experimental setup, as well as the structure quality of deep and ultra deep X-ray lithographic microstructures are described.

Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2018-01-01

Free-standing solid polymer nanocomposite (PEO-PVC)  +  LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ~5  ×  10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ~3.5 V. The ion transference number has been estimated, t ion  =  0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 °C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (µ), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (σ) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a rechargeable lithium-ion battery system.

Jumbo squid beaks: inspiration for design of robust organic composites.

PubMed

Miserez, Ali; Li, Youli; Waite, J Herbert; Zok, Frank

2007-01-01

The hard tissues found in some invertebrate marine organisms represent intriguing paradigms for robust, lightweight materials. The present study focuses on one such tissue: that comprising the beak of the jumbo squid (Dosidicus gigas). Its main constituents are chitin fibers (15-20wt.%) and histidine- and glycine-rich proteins (40-45%). Notably absent are mineral phases, metals and halogens. Despite being fully organic, beak hardness and stiffness are at least twice those of the most competitive synthetic organic materials (notably engineering polymers) and comparable to those of Glycera and Nereis jaws. Furthermore, the combination of hardness and stiffness makes the beaks more resistant to plastic deformation when in contact with blunt abrasives than virtually all metals and polymers. The 3,4-dihydroxy-l-phenylalanine and abundant histidine content in the beak proteins as well as the pigmented hydrolysis-resistant residue are suggestive of aromatic cross-linking. A high cross-linking density between the proteins and chitin may be the single most important determinant of hardness and stiffness in the beak. Beak microstructure is characterized by a lamellar arrangement of the constituents, with a weak interface that promotes crack deflection and endows the structure with high fracture toughness. The susceptibility of this microstructure to cracking along these interfaces from contact stresses at the external surface is mitigated by the presence of a protective coating.

Metal catalyzed synthesis of hyperbranched ethylene and/or .alpha.-olefin polymers

DOEpatents

Sen, Ayusman; Kim, Jang Sub; Pawlow, James H.; Murtuza, Shahid; Kacker, Smita; Wojcinski, III, Louis M.

2001-01-01

Oily hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin, and a method for their synthesis, are disclosed. The polymers have non-regular microstructures and are characterized by a ratio ({character pullout})of methyl hydrogens centered around 0.85 ppm on the 1H-NMR spectra of the polymers relative to total aliphatic hydrogens of from about 0.40 to about 0.65 for polymers derived from ethylene or butene, and a ratio ({character pullout})of from greater than 0.50 to about 0.65 for polymers derived from propylene. A method for grafting hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin onto aromatic rings in organic molecules and polymers, and the resulting grafted materials, are also disclosed. The hyperbranched polymers and grafted materials are useful, for example, as lubricants and lubricant additives.

Development of refractive X-ray focusing optics at Diamond Light Source

NASA Astrophysics Data System (ADS)

Alianelli, L.; Sawhney, K. J. S.; Loader, I. M.; Jenkins, D. W. K.; Stevens, R.; Snigirev, A.; Snigireva, I.

2007-09-01

The Diamond Optics & Metrology Group and the collaborators at the STFC Central Microstructure Facility have initiated a program for the design and fabrication of in-line micro- and nano-focusing optics for synchrotron radiation beamlines. The first type of optics fabricated is a kinoform lens in silicon on the same model proposed by K. Evans- Lutterodt et al [Opt. Expr. 11 (2003) 919.]. The fabrication utilised ultra high resolution electron beam lithographic patterning of an electron sensitive SU8 polymer and deep reactive ion etching of silicon. The first test of the focusing properties was performed at the ESRF BM5 optics beamline. In this paper we present details on the design and fabrication, and discuss the test results.

Towards a physics-based multiscale modelling of the electro-mechanical coupling in electro-active polymers.

PubMed

Cohen, Noy; Menzel, Andreas; deBotton, Gal

2016-02-01

Owing to the increasing number of industrial applications of electro-active polymers (EAPs), there is a growing need for electromechanical models which accurately capture their behaviour. To this end, we compare the predicted behaviour of EAPs undergoing homogeneous deformations according to three electromechanical models. The first model is a phenomenological continuum-based model composed of the mechanical Gent model and a linear relationship between the electric field and the polarization. The electrical and the mechanical responses according to the second model are based on the physical structure of the polymer chain network. The third model incorporates a neo-Hookean mechanical response and a physically motivated microstructurally based long-chains model for the electrical behaviour. In the microstructural-motivated models, the integration from the microscopic to the macroscopic levels is accomplished by the micro-sphere technique. Four types of homogeneous boundary conditions are considered and the behaviours determined according to the three models are compared. For the microstructurally motivated models, these analyses are performed and compared with the widely used phenomenological model for the first time. Some of the aspects revealed in this investigation, such as the dependence of the intensity of the polarization field on the deformation, highlight the need for an in-depth investigation of the relationships between the structure and the behaviours of the EAPs at the microscopic level and their overall macroscopic response.

The Influence of Chain Microstructure of Biodegradable Copolyesters Obtained with Low-Toxic Zirconium Initiator to In Vitro Biocompatibility

PubMed Central

Orchel, Arkadiusz; Kasperczyk, Janusz; Marcinkowski, Andrzej; Pamula, Elzbieta; Orchel, Joanna; Bielecki, Ireneusz

2013-01-01

Because of the wide use of biodegradable materials in tissue engineering, it is necessary to obtain biocompatible polymers with different mechanical and physical properties as well as degradation ratio. Novel co- and terpolymers of various composition and chain microstructure have been developed and applied for cell culture. The aim of this study was to evaluate the adhesion and proliferation of human chondrocytes to four biodegradable copolymers: lactide-coglycolide, lactide-co-ε-caprolactone, lactide-co-trimethylene carbonate, glycolide-co-ε-caprolactone, and one terpolymer glycolide-colactide-co-ε-caprolactone synthesized with the use of zirconium acetylacetonate as a nontoxic initiator. Chain microstructure of the copolymers was analyzed by means of 1H and 13C NMR spectroscopy and surface properties by AFM technique. Cell adhesion and proliferation were determined by CyQUANT Cell Proliferation Assay Kit. After 4 h the chondrocyte adhesion on the surface of studied materials was comparable to standard TCPS. Cell proliferation occurred on all the substrates; however, among the studied polymers poly(L-lactide-coglycolide) 85 : 15 that characterized the most blocky structure best supported cell growth. Chondrocytes retained the cell membrane integrity evaluated by the LDH release assay. As can be summarized from the results of the study, all the studied polymers are well tolerated by the cells that make them appropriate for human chondrocytes growth. PMID:24062998

Synergistic effect of polyaniline coverage and surface microstructure on the inhibition of Pseudomonas aeruginosa biofilm formation.

PubMed

Gallarato, L A; Mulko, L E; Dardanelli, M S; Barbero, C A; Acevedo, D F; Yslas, E I

2017-02-01

Biofilm Formation is a survival strategy for microorganisms to adapt to their environment. Microbial cells in biofilm become tolerant and resistant to antibiotics and immune responses, increasing the difficulties for the clinical treatment of microbial infections. The surface chemistry and the micro/nano-topography of solid interfaces play a major role in mediating microorganism activity and adhesion. The effect of the surface chemical composition and topography on the adhesion and viability of Pseudomonas aeruginosa was studied. Polymeric (polyethylene terephthalate) surfaces were covered with a conducting polymer (polyaniline, PANI) film by in-situ polymerization and microstructured by Direct Laser Interference Patterning (DLIP). The viability of Pseudomonas aeruginosa on the different surfaces was investigated. The physicochemical properties of the surfaces were characterized by water contact angle measurements, scanning electron microscopy and atomic force microscopy. Bacterial biofilms were imaged by atomic force and scanning electron microscopies. The bacterial viability decreased on PANI compared with the substrate (polyethylene terephthalate) and it decreased even more upon micro-structuring the PANI films. In addition, the biofilm reduction could be improved using polymers with different chemical composition and/or the same polymer with different topographies. Both methods presented diminish the bacterial attachment and biofilm formation. These findings present a high impact related to materials for biomedical engineer applications regarding medical devices, as prostheses or catheters. Copyright © 2016 Elsevier B.V. All rights reserved.

Grayscale lithography-automated mask generation for complex three-dimensional topography

NASA Astrophysics Data System (ADS)

Loomis, James; Ratnayake, Dilan; McKenna, Curtis; Walsh, Kevin M.

2016-01-01

Grayscale lithography is a relatively underutilized technique that enables fabrication of three-dimensional (3-D) microstructures in photosensitive polymers (photoresists). By spatially modulating ultraviolet (UV) dosage during the writing process, one can vary the depth at which photoresist is developed. This means complex structures and bioinspired designs can readily be produced that would otherwise be cost prohibitive or too time intensive to fabricate. The main barrier to widespread grayscale implementation, however, stems from the laborious generation of mask files required to create complex surface topography. We present a process and associated software utility for automatically generating grayscale mask files from 3-D models created within industry-standard computer-aided design (CAD) suites. By shifting the microelectromechanical systems (MEMS) design onus to commonly used CAD programs ideal for complex surfacing, engineering professionals already familiar with traditional 3-D CAD software can readily utilize their pre-existing skills to make valuable contributions to the MEMS community. Our conversion process is demonstrated by prototyping several samples on a laser pattern generator-capital equipment already in use in many foundries. Finally, an empirical calibration technique is shown that compensates for nonlinear relationships between UV exposure intensity and photoresist development depth as well as a thermal reflow technique to help smooth microstructure surfaces.

Small-angle-neutron-scattering from giant water-in-oil microemulsion droplets. II. Polymer-decorated droplets in a quaternary system

NASA Astrophysics Data System (ADS)

Foster, Tobias; Sottmann, Thomas; Schweins, Ralf; Strey, Reinhard

2008-02-01

Amphiphilic block copolymers of the type poly(ethylenepropylene)-co-poly(ethyleneoxide) dramatically enhance the solubilisation efficiency of non-ionic surfactants in microemulsions that contain equal volumes of water in oil. Consequently, the length scale of the microstructure of such bicontinuous microemulsions is dramatically increased up to the order of a few 100nm. In this paper, we show that this so-called efficiency boosting effect can also be applied to water-in-oil microemulsions with droplet microstructure. Such giant water-in-oil microemulsions would provide confined compartments in which chemical reactions of biological macromolecules can be performed on a single molecule level. With this motivation we investigated the phase behavior and the microstructure of oil-rich microemulsions containing D2O, n-decane(d22), C10E4 and the amphiphilic block copolymer PEP5-PEO5 [poly(ethylenepropylene)-co-poly(ethyleneoxide), weight per block of 5000g/mol]. We found that 15wt% of water can be solubilised by 5wt% of surfactant and block copolymer when about 6wt% of surfactant is replaced by the block copolymer. Small-angle-neutron-scattering experiments were performed to determine the length scales and microstructure topologies of the oil-rich microemulsions. To analyze the scattering data, we derived a novel form factor that also takes into account the scattering contribution of the hydrophobic part of the block copolymer molecules that reside in the surfactant shell. The quantitative analysis of the scattering data with this form factor shows that the radius of the largest droplets amounts up to 30nm. The novel form factor also yielded qualitative information on the stretching of the polymer chains in dependence on the polymer surface density and the droplet radius.

A Comparison of Water Diffusion in Polymer Based Fuel Cell and Reverse Osmosis Membrane Materials

NASA Astrophysics Data System (ADS)

Soles, Christopher; Frieberg, Bradley; Tarver, Jacob; Tyagi, Madhusudan; Jeong, Cheol; Chan, Edwin; Stafford, Christopher

Hydrated polymer membranes are critical in both fuel cells and water filtration and desalination. In both of these applications the membrane function (selectively transporting or separating ions) is coupled with the transport of water through the membrane. There is a significant need to understand the nature by which the water and ions distribute and move through these membranes. This presentation compares the transport mechanisms in in an ion containing block copolymer alkaline fuel cell membrane with that of a polyamide membrane that is used as the active layer in a reverse osmosis water desalination membrane. Small angle neutron scattering measurements are used to locally probe how water swells the different materials and quantitatively describe the distribution of water within the membrane microstructures. Quasielastic neutron scattering measurements are then used to separate the polymer dynamics of the host membranes from the dynamics of the water inside the membranes. This reveals that water moves at least an order of magnitude slower through the ion containing fuel cell membrane materials, consistent with a solution-diffusion model, while the water in the polyamide membranes moves faster, consistent with a pore-flow diffusion mechanism. These insights will be discussed in terms of a coupling of the water and polymer dynamics and design cues for high performance membrane materials.

Anisotropic wetting of microstructured surfaces as a function of surface chemistry.

PubMed

Neuhaus, Sonja; Spencer, Nicholas D; Padeste, Celestino

2012-01-01

In order to study the influence of surface chemistry on the wetting of structured surfaces, microstructures consisting of grooves or squares were produced via hot embossing of poly(ethylene-alt-tetrafluoroethylene) ETFE substrates. The structured substrates were modified with polymer brushes, thereby changing their surface functionality and wettability. Water droplets were most strongly pinned to the structure when the surface was moderately hydrophilic, as in the case of poly(4-vinylpyridine) (P4VP) or poly(vinyl(N-methyl-2-pyridone) (PVMP) brush-modified substrates. As a result, the droplet shape was determined by the features of the microstructure. The water contact angles (CA) were considerably higher than on flat surfaces and differed, in the most extreme case, by 37° when measured on grooved substrates, parallel and perpendicular to the grooves. On hydrophobic substrates (pristine ETFE), the same effects were observed but were much less pronounced. On very hydrophilic sampes (those modified with poly(N-methyl-vinylpyridinium) (QP4VP)), the microstructure had no influence on the drop shape. These findings are explained by significant differences in apparent and real contact angles at the relatively smooth edges of the embossed structures. Finally, the highly anisotropic grooved microstructure was combined with a gradient in polymer brush composition and wettability. In the case of a parallel alignment of the gradient direction to the grooves, the directed spreading of water droplets could be observed. © 2011 American Chemical Society

Design of high strength polymer metal interfaces by laser microstructured surfaces

NASA Astrophysics Data System (ADS)

Steinert, P.; Dittes, A.; Schimmelpfennig, R.; Scharf, I.; Lampke, T.; Schubert, A.

2018-06-01

In the areas of automotive, aeronautics and civil structures, lightweight construction is a current and a future need. Thus, multi material design has rapidly grown in importance, especially hybrid materials based on fiber reinforced plastics and aluminum offer great potential. Therefore, mechanical interlocking is a convenient way of designing the interface. Laser structuring is already used to generate a variety of surface topographies leading to high bond strengths. This paper investigates different laser structures aiming on highest joint strengths for aluminum and glass fiber reinforced polyamide 6 interfaces. Self-organizing pin structures comprised by additional micro/nano features as well as drilled hole structures, both ranging on the micrometer range, are compared to corundum blasting as a standard method for surface conditioning. For the presented surface structures, thermal joining and ultrasonic assisted joining are regarded towards their potential for an optimum joint design.

Electrospun Polymer Fibers for Electronic Applications

PubMed Central

Luzio, Alessandro; Canesi, Eleonora Valeria; Bertarelli, Chiara; Caironi, Mario

2014-01-01

Nano- and micro- fibers of conjugated polymer semiconductors are particularly interesting both for applications and for fundamental research. They allow an investigation into how electronic properties are influenced by size confinement and chain orientation within microstructures that are not readily accessible within thin films. Moreover, they open the way to many applications in organic electronics, optoelectronics and sensing. Electro-spinning, the technique subject of this review, is a simple method to effectively form and control conjugated polymer fibers. We provide the basics of the technique and its recent advancements for the formation of highly conducting and high mobility polymer fibers towards their adoption in electronic applications. PMID:28788493

Chemical Immobilization Effect on Lithium Polysulfides for Lithium-Sulfur Batteries.

PubMed

Li, Caixia; Xi, Zhucong; Guo, Dexiang; Chen, Xiangju; Yin, Longwei

2018-01-01

Despite great progress in lithium-sulfur batteries (LSBs), great obstacles still exist to achieve high loading content of sulfur and avoid the loss of active materials due to the dissolution of the intermediate polysulfide products in the electrolyte. Relationships between the intrinsic properties of nanostructured hosts and electrochemical performance of LSBs, especially, the chemical interaction effects on immobilizing polysulfides for LSB cathodes, are discussed in this Review. Moreover, the principle of rational microstructure design for LSB cathode materials with strong chemical interaction adsorbent effects on polysulfides, such as metallic compounds, metal particles, organic polymers, and heteroatom-doped carbon, is mainly described. According to the chemical immobilizing mechanism of polysulfide on LSB cathodes, three kinds of chemical immobilizing effects, including the strong chemical affinity between polar host and polar polysulfides, the chemical bonding effect between sulfur and the special function groups/atoms, and the catalytic effect on electrochemical reaction kinetics, are thoroughly reviewed. To improve the electrochemical performance and long cycling life-cycle stability of LSBs, possible solutions and strategies with respect to the rational design of the microstructure of LSB cathodes are comprehensively analyzed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic-inorganic composites designed for biomedical applications.

PubMed

Miyazaki, Toshiki; Ishikawa, Kunio; Shirosaki, Yuki; Ohtsuki, Chikara

2013-01-01

Several varieties of ceramics, such as Bioglass-type glasses, sintered hydroxyapatite and glass-ceramic A-W, exhibit specific biological affinity, i.e., direct bonding to surrounding bone, when implanted in bony defects. These bone-bonding ceramics are called bioactive ceramics and are utilized as important bone substitutes in the medical field. However, there is a limitation to their clinical applications because of their inappropriate mechanical properties. Natural bone takes a kind of organic-inorganic composite, where apatite nanocrystals are precipitated on collagen fibers. Therefore, problems with the bioactive ceramics can be solved by material design based on the composites. In this paper, current research topics on the development of bioactive organic-inorganic composites inspired by actual bone microstructure have been reviewed in correlation with preparation methods and various properties. Several kinds of inorganic components have been found to exhibit bioactivity in the body environment. Combination of the inorganic components with various organic polymers enables the development of bioactive organic-inorganic composites. In addition, novel biomedical applications of the composites to drug delivery systems, scaffolds for tissue regeneration and injectable biomaterials are available by combining drugs or biological molecules with appropriate control of its microstructure.

Mechanisms of transport and electron transfer at conductive polymer/liquid interfaces

NASA Astrophysics Data System (ADS)

Ratcliff, Erin

Organic semiconductors (OSCs) have incredible prospects for next-generation, flexible electronic devices including bioelectronics, thermoelectrics, opto-electronics, and energy storage and conversion devices. Yet many fundamental challenges still exist. First, solution processing prohibits definitive control over microstructure, which is fundamental for controlling electrical, ionic, and thermal transport properties. Second, OSCs generally suffer from poor electrical conductivities due to a combination of low carriers and low mobility. Third, polymeric semiconductors have potential-dependent, dynamically evolving electronic and chemical states, leading to complex interfacial charge transfer properties in contact with liquids. This talk will focus on the use of alternative synthetic strategies of oxidative chemical vapor deposition and electrochemical deposition to control physical, electronic, and chemical structure. We couple our synthetic efforts with energy-, time-, and spatially resolved spectroelectrochemical and microscopy techniques to understand the critical interfacial chemistry-microstructure-property relationships: first at the macroscale, and then moving towards the nanoscale. In particular, approaches to better understand electron transfer events at polymer/liquid interfaces as a function of: 1.) chemical composition; 2.) electronic density of states (DOS); and 3.) crystallinity and microstructure will be discussed.

Coherent photoluminescence excitation spectroscopy of semicrystalline polymeric semiconductors

NASA Astrophysics Data System (ADS)

Silva, Carlos; Grégoire, Pascal; Thouin, Félix

In polymeric semiconductors, the competition between through-bond (intrachain) and through-space (interchain) electronic coupling determines two-dimensional spatial coherence of excitons. The balance of intra- and interchain excitonic coupling depends very sensitively on solid-state microstructure of the polymer film (polycrystalline, semicrystalline with amorphous domains, etc.). Regioregular poly(3-hexylthiophene) has emerged as a model material because its photoluminescence (PL) spectral lineshape reveals intricate information on the magnitude of excitonic coupling, the extent of energetic disorder, and on the extent to which the disordered energy landscape is correlated. I discuss implementation of coherent two-dimensional electronic spectroscopy. We identify cross peaks between 0-0 and 0-1 excitation peaks, and we measure their time evolution, which we interpret within the context of a hybrid HJ aggregate model. By measurement of the homogeneous linewidth in diverse polymer microstructures, we address the nature of optical transitions within such hynbrid aggregate model. These depend strongly on sample processing, and I discuss the relationship between microstructure, steady-state absorption and PL spectral lineshape, and 2D coherent PL excitation spectral lineshapes.

Porous Graphene Microflowers for High-Performance Microwave Absorption

NASA Astrophysics Data System (ADS)

Chen, Chen; Xi, Jiabin; Zhou, Erzhen; Peng, Li; Chen, Zichen; Gao, Chao

2018-06-01

Graphene has shown great potential in microwave absorption (MA) owing to its high surface area, low density, tunable electrical conductivity and good chemical stability. To fully realize graphene's MA ability, the microstructure of graphene should be carefully addressed. Here we prepared graphene microflowers (Gmfs) with highly porous structure for high-performance MA filler material. The efficient absorption bandwidth (reflection loss ≤ -10 dB) reaches 5.59 GHz and the minimum reflection loss is up to -42.9 dB, showing significant increment compared with stacked graphene. Such performance is higher than most graphene-based materials in the literature. Besides, the low filling content (10 wt%) and low density (40-50 mg cm-3) are beneficial for the practical applications. Without compounding with magnetic materials or conductive polymers, Gmfs show outstanding MA performance with the aid of rational microstructure design. Furthermore, Gmfs exhibit advantages in facile processibility and large-scale production compared with other porous graphene materials including aerogels and foams.

Photosensitized oxidation of unsaturated polymers

NASA Technical Reports Server (NTRS)

Golub, M. A.

1979-01-01

The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

Study Of Nondestructive Techniques For Testing Composites

NASA Technical Reports Server (NTRS)

Roth, D.; Kautz, H.; Draper, S.; Bansal, N.; Bowles, K.; Bashyam, M.; Bishop, C.

1995-01-01

Study evaluates some nondestructive methods for characterizing ceramic-, metal-, and polymer-matrix composite materials. Results demonstrated utility of two ultrasonic methods for obtaining quantitative data on microstructural anomalies in composite materials.

Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge.

PubMed

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-10-21

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm(-1)). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge

NASA Astrophysics Data System (ADS)

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-09-01

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm-1). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

Small Molecule Acceptor and Polymer Donor Crystallinity and Aggregation Effects on Microstructure Templating: Understanding Photovoltaic Response in Fullerene-Free Solar Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eastham, Nicholas D.; Dudnik, Alexander S.; Aldrich, Thomas J.

Perylenediimide (PDI) small molecule acceptor (SMA) crystallinity and donor polymer aggregation and crystallinity effects on bulk-heterojunction microstructure and polymer solar cell (PSC) performance are systematically investigated. Two highperformance polymers, semicrystalline poly[5-(2-hexyldodecyl)-4Hthieno[3,4-c]pyrrole-4,6(5H)-dione-1,3-yl-alt-4,4''dodecyl-2,2':5',2''- terthiophene-5,5''-diyl] (PTPD3T or D1) and amorphous poly{4,8- bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene- 2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-2-carboxylate-2,6-diyl) (PBDTT-FTTE or D2), are paired with three PDI-based SMAs (A1-A3) of differing crystallinity (A1 is the most, A3 is the least crystalline). The resulting PSC performance trends are strikingly different from those of typical fullerene-based PSCs and are highly material-dependent. The present trends reflect synergistic aggregation propensities between the SMA and polymer components. Importantly, the active layer morphology is templatedmore » by the PDI in some blends and by the polymer in others, with the latter largely governed by the polymer aggregation. Thus, PTPD3T templating capacity increases as self-aggregation increases (greater Mn), optimizing PSC performance with A2, while A3-based cells exhibit an inverse relationship between polymer aggregation and performance, which is dramatically different from fullerene-based PSCs. For PBDTT-FTTE, A2-based cells again deliver the highest PCEs of ~5%, but here both A2 and PBDTT-FTTE (medium Mn) template the morphology. Overall, the present results underscore the importance of nonfullerene acceptor aggregation for optimizing PSC performance and offer guidelines for pairing SMAs with acceptable donor polymers.« less

Stirring Up Acceptor Phase and Controlling Morphology via Choosing Appropriate Rigid Aryl Rings as Lever Arms in Symmetry-Breaking Benzodithiophene for High-Performance Fullerene and Fullerene-Free Polymer Solar Cells.

PubMed

Liu, Deyu; Wang, Junyi; Gu, Chunyang; Li, Yonghai; Bao, Xichang; Yang, Renqiang

2018-02-01

Two series of new polymers with medium and wide bandgaps to match fullerene (PC 71 BM) and fullerene-free 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC) acceptors are designed and synthesized, respectively. For constructing the key donor building blocks, the effective symmetry-breaking strategy is employed. Two common aromatic rings (thiophene and benzene) are chosen as one side substituted groups in the asymmetric benzodithiophene (BDT) monomers. In addition, another rigid benzene ring is inserted between aryl and thioether in the side chains, which results in larger twisting and destroying the aggregation and forming longer lever arms. As a result, highly ordered polymers (PBDTsTh-FBT and PBDTsPh-FBT) with strong aggregation properties can blend well with roughly spherical PC 71 BM, while amorphous polymers (PBDTsThPh-BDD and PBDTsPhPh-BDD) with long and rigid aryl rings show good miscibility with elongated ITIC, and finally, both devices exhibit excellent power conversion efficiencies over 10%. Thus, it clearly shows that the asymmetric BDT unit is an excellent donor building block to construct highly efficient photovoltaic polymers. Meanwhile, this work demonstrates that it is not necessary that high-performance fullerene-free polymer solar cells (PSCs) require highly ordered microstructures in the blending films, different from the fullerene-based PSCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-Length Scale-Enriched Continuum-Level Material Model for Kevlar (registered trademark)-Fiber-Reinforced Polymer-Matrix Composites

DTIC Science & Technology

2013-03-01

of coarser-scale materials and structures containing Kevlar fibers (e.g., yarns, fabrics, plies, lamina, and laminates ). Journal of Materials...Multi-Length Scale-Enriched Continuum-Level Material Model for Kevlar -Fiber-Reinforced Polymer-Matrix Composites M. Grujicic, B. Pandurangan, J.S...extensive set of molecular-level computational analyses regarding the role of various microstructural/morphological defects on the Kevlar fiber

Self-Lubricating Coatings for Elevated Temperature Applications Using A High-Velocity-Particle-Consolidation (HVPC) Process

DTIC Science & Technology

2008-12-01

Deposition of copper by cold gas dynamic spraying : An investigation of dependence of microstructure and properties of the deposits on the...the deposition of metals, alloys , polymers, and composite powder -materials onto various substrates without significant heating of the spray powders or... Spray method is a relatively new coating method for deposition of metal, alloy , polymer, and/or composite powder material onto

Effect of polymer properties and adherend surfaces on adhesion

NASA Technical Reports Server (NTRS)

Dwight, D. W.; Wightman, J. P.

1976-01-01

High temperature polymer surface characteristics associated with joint strength were evaluated. Selected samples represented composite adherends, aluminum filler and fiber glass carrier cloth. Detailed analysis of fractured joint surfaces revealed unique characteristics typical of the specific adhesive formulations and test conditions. A fracture mechanism model was developed for correlating macroscopic shear strength and microstructure of fracture surfaces. Applications were made to unpublished data on polyimides and fluoropolymers.

Supplement request for Support of MRS Symposium (PECASE: Active Microstructured Polymer Systems)

DTIC Science & Technology

2015-07-06

materials (e.g., gels, polymers, liquids , liquid crystals and photosensitive materials) that can change shape in a controlled response to stimuli. These...Rogers1. 1, , University of Illinois, Urbana, Illinois, USA. Show Abstract 8:45 AM - *XX1.02 New Wonders of Nafion : Shape Memory, Temperature Memory... Liquid Crystal Institute, Kent State University, Kent, Ohio, USA; 5, Department of Electrical and Computer Engineering, University of Idaho, Moscow

Responsive copolymers for enhanced petroleum recovery. Quarterly progress report, March 21, 1995--June 22, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, C.; Hester, R.

Advanced polymer systems that possess microstructural features that are responsive to temperature, electrolyte concentration, and shear conditions are being synthesized which will be superior to polymers presently used for mobility control in enhanced oil recovery. Improved polymer performance is accomplished by controlling hydrophobic or ampholytic interactions between individual polymer chains in solution. Of special interest to our group have been (1) the elucidation of the mechanism of associative thickening and (2) the tailoring of thickeners with reversible associations responsive to changes in pH, ionic strength, temperature, or shear stress. A polymerization technique, termed ``micellar`` polymerization utilizes a surfactant to solubilizemore » a relatively low mole percent of a hydrophobic monomer in water for copolymerization with a hydrophilic monomer. In this report, we examine the role of surfactant-to-monomer ratio (SMR) in the reaction medium on microstructure utilizing the N-[(1- pyrenylsulfonamido)ethyl] acrylamide (APS) monomer as a fluorescent label. Comparison is made with previously reported terpolymers of identical AM/AA compositions with N-(4-decyl)phenylacrylamide as the hydrophobic monomer. Unlike the uncharged copolymer of AM/APS, however, the AM/AA/APS terpolymers of this study do not show intermolecular associative thickening, apparently due to insufficient liaisons of hydrophobic microdomains even at high concentrations of terpolymer.« less

Thermo-optic characteristics of hybrid polymer/silica microstructured optical fiber: An analytical approach

NASA Astrophysics Data System (ADS)

Sharma, Dinesh Kumar; Sharma, Anurag; Tripathi, Saurabh Mani

2018-04-01

Microstructured optical fibers (MOFs) allow a variety of advanced materials to be infiltrated in their air-voids for obtaining the increased fiber functionality, and offering a new versatile platform for developing the compact sensors devices. We aim to investigate the thermal characteristics of high-index core triangular hybrid polymer/silica MOFs with circular air-voids infused with polymer by using the analytical field model [1]. We demonstrate that infiltration of air-voids with polymer, e.g., polydimethylsiloxane (PDMS) can facilitate to tune the fundamental modal properties of MOF such as effective index of the mode, near and the far-field profiles, effective mode area and the numerical aperture over the temperature ranging from 0 °C to 100 °C, for different values of relative air-void ratios. The evolution of the mode shape for a given temperature has been investigated in transition from near-field to far-field regime. We have studied the thermal dependence of splice losses between hybrid MOF and the standard step-index single-mode optical fiber in combination with Fresnel losses. For enhancing the evanescent field interactions, we have evaluated fraction of power associated with fundamental mode of hybrid MOF. We have compared the accuracy of our results with those based on full-vector finite-difference (FD) method, as available in the literature.

Radiation preparation of drug carriers based polyacrylic acid (PAAc) using poly(vinyl pyrrolidone) (PVP) as a template polymer

NASA Astrophysics Data System (ADS)

Abd El-Rehim, H. A.; Hegazy, E. A.; Khalil, F. H.; Hamed, N. A.

2007-01-01

The present study deals with the radiation synthesis of stimuli response hydrophilic polymers from polyacrylic acid (PAAc). To maintain the property of PAAc and control the water swellibility for its application as a drug delivery system, radiation polymerization of AAc in the presence of poly(vinyl pyrrolidone) (PVP) as a template polymer was carried out. Characterization of the prepared PAA/PVP inter-polymer complex was investigated by determining gel content, swelling property, hydrogel microstructure and the release rate of caffeine as a model drug. The release rate of caffeine from the PAA/PVP inter-polymer complexes showed pH-dependency, and seemed to be mainly controlled by the dissolution rate of the complex above a p Ka of PAAc. The prepared inter-polymer complex could be used for application as drug carriers.

A finite element approach to self-consistent field theory calculations of multiblock polymers

NASA Astrophysics Data System (ADS)

Ackerman, David M.; Delaney, Kris; Fredrickson, Glenn H.; Ganapathysubramanian, Baskar

2017-02-01

Self-consistent field theory (SCFT) has proven to be a powerful tool for modeling equilibrium microstructures of soft materials, particularly for multiblock polymers. A very successful approach to numerically solving the SCFT set of equations is based on using a spectral approach. While widely successful, this approach has limitations especially in the context of current technologically relevant applications. These limitations include non-trivial approaches for modeling complex geometries, difficulties in extending to non-periodic domains, as well as non-trivial extensions for spatial adaptivity. As a viable alternative to spectral schemes, we develop a finite element formulation of the SCFT paradigm for calculating equilibrium polymer morphologies. We discuss the formulation and address implementation challenges that ensure accuracy and efficiency. We explore higher order chain contour steppers that are efficiently implemented with Richardson Extrapolation. This approach is highly scalable and suitable for systems with arbitrary shapes. We show spatial and temporal convergence and illustrate scaling on up to 2048 cores. Finally, we illustrate confinement effects for selected complex geometries. This has implications for materials design for nanoscale applications where dimensions are such that equilibrium morphologies dramatically differ from the bulk phases.

Preparation and evaluation of molecularly imprinted polymer for selective recognition and adsorption of gossypol.

PubMed

Zhi, Keke; Wang, Lulu; Zhang, Yagang; Zhang, Xuemin; Zhang, Letao; Liu, Li; Yao, Jun; Xiang, Wei

2018-03-01

Molecularly imprinted polymers (MIPs) were designed and prepared via bulk thermal polymerization with gossypol as the template molecule and dimethylaminoethyl methacrylate as the functional monomer. The morphology and microstructures of MIPs were characterized by scanning electron microscope and Brunauer-Emmett-Teller surface areas. Static adsorption tests were performed to evaluate adsorption behavior of gossypol by the MIPs. It was found that adsorption kinetics and adsorption isotherms data of MIPs for gossypol were fit well with the pseudo-second-order model and Freundlich model, respectively. Scatchard analysis showed that heterogeneous binding sites were formed in the MIPs, including lower-affinity binding sites with the maximum adsorption of 252 mg/g and higher-affinity binding sites with the maximum adsorption of 632 mg/g. Binding studies also revealed that MIPs had favorable selectivity towards gossypol compared with non-imprinted polymers. Furthermore, adsorption capacity of MIPs maintained above 90% after 5 regeneration cycles, indicating MIPs were recyclable and could be used multiple times. These results demonstrated that prepared MIPs could be a promising functional material for selective adsorption of gossypol. Copyright © 2017 John Wiley & Sons, Ltd.

A finite element approach to self-consistent field theory calculations of multiblock polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ackerman, David M.; Delaney, Kris; Fredrickson, Glenn H.

Self-consistent field theory (SCFT) has proven to be a powerful tool for modeling equilibrium microstructures of soft materials, particularly for multiblock polymers. A very successful approach to numerically solving the SCFT set of equations is based on using a spectral approach. While widely successful, this approach has limitations especially in the context of current technologically relevant applications. These limitations include non-trivial approaches for modeling complex geometries, difficulties in extending to non-periodic domains, as well as non-trivial extensions for spatial adaptivity. As a viable alternative to spectral schemes, we develop a finite element formulation of the SCFT paradigm for calculating equilibriummore » polymer morphologies. We discuss the formulation and address implementation challenges that ensure accuracy and efficiency. We explore higher order chain contour steppers that are efficiently implemented with Richardson Extrapolation. This approach is highly scalable and suitable for systems with arbitrary shapes. We show spatial and temporal convergence and illustrate scaling on up to 2048 cores. Finally, we illustrate confinement effects for selected complex geometries. This has implications for materials design for nanoscale applications where dimensions are such that equilibrium morphologies dramatically differ from the bulk phases.« less

Fluorescence hydrogen peroxide probe based on a microstructured polymer optical fiber modified with a titanium dioxide film.

PubMed

Li, Dongdong; Wang, Lili

2010-05-01

A highly sensitive microstructured polymer optical fiber (MPOF) probe for hydrogen peroxide was made by forming a rhodamine 6G-doped titanium dioxide film on the side walls of array holes in an MPOF. It was found that hydrogen peroxide only has a response to the MPOF probe in a certain concentration of potassium iodide in sulfuric acid solution. The calibration graph of fluorescence intensity versus hydrogen peroxide concentration is linear in the range of 1.6 x 10(-7) mol/L to 9.6 x 10(-5) mol/L. The method, with high sensitivity and a wide linear range, has been applied to the determination of trace amounts of hydrogen peroxide in a few real samples, such as rain water and contact lens disinfectant, with satisfactory results.

Recent advances in the chemical modification of unsaturated polymers

NASA Technical Reports Server (NTRS)

Schulz, D. N.; Turner, S. R.; Golub, M. A.

1982-01-01

The present discussion has the objective to update the most comprehensive reviews on the considered subject and to fill in the gaps of less complete, but more modern treatments. Only simple chemical functionalization or structural modification of unsaturated polymers are covered, and the literature of diene polymer modification since 1974 is emphasized. Attention is given to hydrogenation, halogenation and hydrohalogenation, cyclization, cis-trans isomerization, epoxidation, ene and other cycloaddition reactions, sulfonation, carboxylation, phosphonylation, sulfenyl chloride addition, carbene addition, metalation, and silylation. It is pointed out that modern synthetic reagents and catalysts have been advantageously employed to improve process and/or product quality. Synthetic techniques have been refined to allow the selective modification of specific polymer microstructures or blocks.

Fabrication of fillable microparticles and other complex 3D microstructures

NASA Astrophysics Data System (ADS)

McHugh, Kevin J.; Nguyen, Thanh D.; Linehan, Allison R.; Yang, David; Behrens, Adam M.; Rose, Sviatlana; Tochka, Zachary L.; Tzeng, Stephany Y.; Norman, James J.; Anselmo, Aaron C.; Xu, Xian; Tomasic, Stephanie; Taylor, Matthew A.; Lu, Jennifer; Guarecuco, Rohiverth; Langer, Robert; Jaklenec, Ana

2017-09-01

Three-dimensional (3D) microstructures created by microfabrication and additive manufacturing have demonstrated value across a number of fields, ranging from biomedicine to microelectronics. However, the techniques used to create these devices each have their own characteristic set of advantages and limitations with regards to resolution, material compatibility, and geometrical constraints that determine the types of microstructures that can be formed. We describe a microfabrication method, termed StampEd Assembly of polymer Layers (SEAL), and create injectable pulsatile drug-delivery microparticles, pH sensors, and 3D microfluidic devices that we could not produce using traditional 3D printing. SEAL allows us to generate microstructures with complex geometry at high resolution, produce fully enclosed internal cavities containing a solid or liquid, and use potentially any thermoplastic material without processing additives.

Long-term aging of Ag/a-C:H:O nanocomposite coatings in air and in aqueous environment

NASA Astrophysics Data System (ADS)

Drábik, Martin; Pešička, Josef; Biederman, Hynek; Hegemann, Dirk

2015-04-01

Nanocomposite coatings of silver particles embedded in a plasma polymer matrix possess interesting properties depending on their microstructure. The film microstructure is affected among others also by the RF power supplied during the deposition, as shown by transmission electron microscopy. The optical properties are characterized by UV-vis-NIR spectroscopy. An anomalous optical absorption peak from the Ag nanoparticles is observed and related to the microstructure of the nanocomposite films. Furthermore, a long-term aging of the coatings is studied in-depth in ambient air and in aqueous environments. It is shown that the studied films are not entirely stable. The deposition conditions and the microstructure of the films affect the processes taking place during their aging in both environments.

Multilevel Investigation of Charge Transport in Conjugated Polymers.

PubMed

Dong, Huanli; Hu, Wenping

2016-11-15

Conjugated polymers have attracted the world's attentions since their discovery due to their great promise for optoelectronic devices. However, the fundamental understanding of charge transport in conjugated polymers remains far from clear. The origin of this challenge is the natural disorder of polymers with complex molecular structures in the solid state. Moreover, an effective way to examine the intrinsic properties of conjugated polymers is absent. Optoelectronic devices are always based on spin-coated films. In films, polymers tend to form highly disordered structures at nanometer to micrometer length scales due to the high degree of conformational freedom of macromolecular chains and the irregular interchain entanglement, thus typically resulting in much lower charge transport properties than their intrinsic performance. Furthermore, a subtle change of processing conditions may dramatically affect the film formation-inducing large variations in the morphology, crystallinity, microstructure, molecular packing, and alignment, and finally varying the effective charge transport significantly and leading to great inconsistency over an order of magnitude even for devices based on the same polymer semiconductor. Meanwhile, the charge transport mechanism in conjugated polymers is still unclear and its investigation is challenging based on such complex microstructures of polymers in films. Therefore, how to objectively evaluate the charge transport and probe the charge transport mechanism of conjugated polymers has confronted the world for decades. In this Account, we present our recent progress on multilevel charge transport in conjugated polymers, from disordered films, uniaxially aligned thin films, and single crystalline micro- or nanowires to molecular scale, where a derivative of poly(para-phenylene ethynylene) with thioacetyl end groups (TA-PPE) is selected as the candidate for investigation, which could also be extended to other conjugated polymer systems. Our systematic investigations demonstrated that 3-4 orders higher charge transport properties could be achieved with the improvement of polymer chain order and confirmed efficient charge transport along the conjugated polymer backbones. Moreover, with downscaling to molecular scale, many novel phenomena were observed such as the largely quantized electronic structure for an 18 nm-long TA-PPE and the modulation of the redox center of tetrathiafulvalene (TTF) units on tunneling charge transport, which opens the door for conjugated polymers used in nanometer quantum devices. We hope the understanding of charge transport in PPE and its related conjugated polymer at multilevel scale in this Account will provide a new method to sketch the charge transport properties of conjugated polymers, and new insights into the combination of more conjugated polymer materials in the multilevel optoelectronic and other related functional devices, which will offer great promise for the next generation of electronic devices.

Scaling up the Single Transducer Thickness-Independent Ultrasonic Imaging Method for Accurate Characterization of Microstructural Gradients in Monolithic and Composite Tubular Structures

NASA Technical Reports Server (NTRS)

Roth, Don J.; Carney, Dorothy V.; Baaklini, George Y.; Bodis, James R.; Rauser, Richard W.

1998-01-01

Ultrasonic velocity/time-of-flight imaging that uses back surface reflections to gauge volumetric material quality is highly suited for quantitative characterization of microstructural gradients including those due to pore fraction, density, fiber fraction, and chemical composition variations. However, a weakness of conventional pulse-echo ultrasonic velocity/time-of-flight imaging is that the image shows the effects of thickness as well as microstructural variations unless the part is uniformly thick. This limits this imaging method's usefulness in practical applications. Prior studies have described a pulse-echo time-of-flight-based ultrasonic imaging method that requires using a single transducer in combination with a reflector plate placed behind samples that eliminates the effect of thickness variation in the image. In those studies, this method was successful at isolating ultrasonic variations due to material microstructure in plate-like samples of silicon nitride, metal matrix composite, and polymer matrix composite. In this study, the method is engineered for inspection of more complex-shaped structures-those having (hollow) tubular/curved geometry. The experimental inspection technique and results are described as applied to (1) monolithic mullite ceramic and polymer matrix composite 'proof-of-concept' tubular structures that contain machined patches of various depths and (2) as-manufactured monolithic silicon nitride ceramic and silicon carbide/silicon carbide composite tubular structures that might be used in 'real world' applications.

Growth of polymer-metal nanocomposites by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Röder, Johanna; Faupel, Jörg; Krebs, Hans-Ulrich

2008-12-01

Complex polymer-metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.

Processing and properties of ceramic matrix-polymer composites for dental applications

NASA Astrophysics Data System (ADS)

Huang, Hsuan Yao

The basic composite structure of natural hard tissue was used to guide the design and processing of dental restorative materials. The design incorporates the methodology of using inorganic minerals as the main structural phase reinforced with a more ductile but tougher organic phase. Ceramic-polymer composites were prepared by slip casting a porous ceramic structure, heating and chemical treating the porous preform, infiltrating with monomer and then curing. The three factors that determined the mechanical properties of alumina-polymer composites were the type of polymer used, the method of silane treatments, and the type of bond between particles in the porous preforms. Without the use of silane coupling agents, the composites were measured to have a lower strength. The composite with a more "flexible" porous alumina network had a greater ability to plastically dissipate the energy of propagating cracks. However, the aggressive nature of the alumina particles on opposing enamel requires that these alumina-polymer composites have a wear compatible coating for practical application. A route to dense bioactive apatite wollastonite glass ceramics (AWGC)-polymer composites was developed. The problems associated with glass dissolution into the aqueous medium for slip casting were overcome with the use of silane. The role of heating rate and development of ceramic compact microstructure on composite properties was explored. In general, if isothermal heating was not applied, decreasing heating rate increased glass crystallinity and particle-particle fusion, but decreased pore volume. Also composite strength and fracture toughness decreased while modulus and hardness increased with decreasing heating rate. If isothermal heating was applied, glass crystallinity, pore content, and composite mechanical properties showed relatively little change regardless of the initial heating rate. The potential of AWGC-polymer composites for dental and implant applications was explored. Strengths and toughnesses were not severely degraded by immersion in simulated body fluids up to 30 days. The composite elastic modulus approached that of hard tissues and its wear behavior with opposing tooth was excellent. Growth of apatite over the entire composite surface was achieved in SBF. Growth of apatite in human whole saliva was achieved on the bioactive glass surface, but not on the composite surface.

Controlled Growth of Polypyrrole on Microelectrodes

NASA Astrophysics Data System (ADS)

Kannan, Bhuvaneswari; Williams, David E.; Travas-Sejdic, Jandranka

2009-07-01

Electrochemical growth of a conducting polymer generally leads to a microstructure which is an irregular assembly of irregular spheres, generally taken to be indicative of a diffusion-limited aggregation in which oligomers generated at or near the electrode aggregate into particles that in turn aggregate onto the electrode. We have explored the possibilities for controlling this growth mode by using short current pulses to form the polymer. We illustrate the alteration in growth morphology achievable by the use of different pulse sequences. In particular, we show the possibility to grow isolated dendrites (`nanowires') of conducting polymer on an electrode surface.

Origin of dielectric relaxor behavior in PVDF-based copolymer and terpolymer films

NASA Astrophysics Data System (ADS)

Pramanick, Abhijit; Osti, Naresh C.; Jalarvo, Niina; Misture, Scott T.; Diallo, Souleymane Omar; Mamontov, Eugene; Luo, Y.; Keum, Jong-Kahk; Littrell, Ken

2018-04-01

Relaxor ferroelectrics exhibit frequency-dispersion of their dielectric permittivity peak as a function of temperature, the origin of which has been widely debated. Microscopic understanding of such behavior for polymeric ferroelectrics has presented new challenges since unlike traditional ceramic ferroelectrics, dielectric relaxation in polymers is a consequence of short-range molecular dynamics that are difficult to measure directly. Here, through careful analysis of atomic-level H-atom dynamics as determined by Quasi-elastic Neutron Scattering (QENS), we show that short-range molecular dynamics within crystalline domains cannot explain the macroscopic frequency-dispersion of dielectric properties observed in prototypical polyvinylidene-fluoride (PVDF)-based relaxor ferroelectrics. Instead, from multiscale quantitative microstructural characterization, a clear correlation between the amount of crystalline-amorphous interfaces and dielectric relaxation is observed, which indicates that such interfaces play a central role. These results provide critical insights into the role of atomic and microscopic structures towards relaxor behavior in ferroelectric polymers, which will be important for their future design.

Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide

PubMed Central

Zhao, Xiaoli; Xu, Zhen; Zheng, Bingna; Gao, Chao

2013-01-01

Nacre realizes strength and toughness through hierarchical designs with primary “brick and mortar” structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0–100%), and proposed an equation to depict the relationship. PMID:24196491

Refractive index sensor based on a polymer fiber directional coupler for low index sensing.

PubMed

Lee, Kwang Jo; Liu, Xiaoqi; Vuillemin, Nelly; Lwin, Richard; Leon-Saval, Sergio G; Argyros, Alexander; Kuhlmey, Boris T

2014-07-14

We propose, numerically analyze and experimentally demonstrate a novel refractive index sensor specialized for low index sensing. The device is based on a directional coupler architecture implemented in a single microstructured polymer optical fiber incorporating two waveguides within it: a single-mode core and a satellite waveguide consisting of a hollow high-index ring. This hollow channel is filled with fluid and the refractive index of the fluid is detected through changes to the wavelength at which resonant coupling occurs between the two waveguides. The sensor design was optimized for both higher sensitivity and lower detection limit, with simulations and experiments demonstrating a sensitivity exceeding 1.4 × 10(3) nm per refractive index unit. Simulations indicate a detection limit of ~2 × 10(-6) refractive index units is achievable. We also numerically investigate the performance for refractive index changes localized at the surface of the holes, a case of particular importance for biosensing.

Sustainable and Continuous Synthesis of Enantiopure l-Amino Acids by Using a Versatile Immobilised Multienzyme System.

PubMed

Velasco-Lozano, Susana; da Silva, Eunice S; Llop, Jordi; López-Gallego, Fernando

2018-02-16

The enzymatic synthesis of α-amino acids is a sustainable and efficient alternative to chemical processes, through which achieving enantiopure products is difficult. To more address this synthesis efficiently, a hierarchical architecture that irreversibly co-immobilises an amino acid dehydrogenase with polyethyleneimine on porous agarose beads has been designed and fabricated. The cationic polymer acts as an irreversible anchoring layer for the formate dehydrogenase. In this architecture, the two enzymes and polymer colocalise across the whole microstructure of the porous carrier. This multifunctional heterogeneous biocatalyst was kinetically characterised and applied to the enantioselective synthesis of a variety of canonical and noncanonical α-amino acids in both discontinuous (batch) and continuous modes. The co-immobilised bienzymatic system conserves more than 50 % of its initial effectiveness after five batch cycles and 8 days of continuous operation. Additionally, the environmental impact of this process has been semiquantitatively calculated and compared with the state of the art. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure Applications for Battery Design | Transportation Research |

Science.gov Websites

NREL Microstructure Applications for Battery Design Microstructure Applications for Battery Design NREL's Computer-Aided Engineering for Electric Drive Vehicle Batteries (CAEBAT) work includes simulating physics at the electrode microstructure level and created a virtual design tool for battery

Effects of microstructural inclusions on fatigue life of polyether ether ketone (PEEK).

PubMed

Simsiriwong, Jutima; Shrestha, Rakish; Shamsaei, Nima; Lugo, Marcos; Moser, Robert D

2015-11-01

In this study, the effects of microstructural inclusions on fatigue life of polyether ether ketone (PEEK) was investigated. Due to the versatility of its material properties, the semi-crystralline PEEK polymer has been increasingly adopted in a wide range of applications particularly as a biomaterial for orthopedic, trauma, and spinal implants. To obtain the cyclic behavior of PEEK, uniaxial fully-reversed strain-controlled fatigue tests were conducted at ambient temperature and at 0.02 mm/mm to 0.04 mm/mm strain amplitudes. The microstructure of PEEK was obtained using the optical and the scanning electron microscope (SEM) to determine the microstructural inclusion properties in PEEK specimen such as inclusion size, type, and nearest neighbor distance. SEM analysis was also conducted on the fracture surface of fatigue specimens to observe microstructural inclusions that served as the crack incubation sites. Based on the experimental strain-life results and the observed microstructure of fatigue specimens, a microstructure-sensitive fatigue model was used to predict the fatigue life of PEEK that includes both crack incubation and small crack growth regimes. Results show that the employed model is applicable to capture microstructural effects on fatigue behavior of PEEK. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effects of Molecular Weight upon Irradiation-Cross-Linked Poly(vinyl alcohol)/Clay Aerogel Properties.

PubMed

Chen, Hong-Bing; Zhao, Yan; Shen, Peng; Wang, Jun-Sheng; Huang, Wei; Schiraldi, David A

2015-09-16

Facile fabrication of mechanically strong poly(vinyl alcohol) (PVOH)/clay aerogel composites through a combination of increasing polymer molecular weights and gamma irradiation-cross-linking is reported herein. The aerogels produced from high polymer molecular weights exhibit significantly increased compressive moduli, similar to the effect of irradiation-induced cross-linking. The required irradiation dose for fabricating strong PVOH composite aerogels with dense microstructure decreased with increasing polymer molecular weight. Neither thermal stability nor flammability was significantly changed by altering the polymer molecular weight or by modest gamma irradiation, but they were highly dependent upon the polymer/clay ratio in the aerogel. Optimization of the mechanical, thermal, and flammability properties of these composite aerogels could therefore be obtained by using relatively low levels of polymer, with very high polymer molecular weight, or lower molecular weight coupled with moderate gamma irradiation. The facile preparation of strong, low flammability aerogels is an alternative to traditional polymer foams in applications where fire safety is important.

Chemical Modification and Structure-property Relationships of Acrylic and Ionomeric Thermoplastic Elastomer Gels

NASA Astrophysics Data System (ADS)

Vargantwar, Pruthesh Hariharrao

Block copolymers (BCs) have remained at the forefront of materials research due to their versatility in applications ranging from hot-melt/pressure-sensitive adhesives and impact modifiers to compatibilizing agents and vibration-dampening/nanotemplating media. Of particular interest are macromolecules composed of two or more chemically dissimilar blocks covalently linked together to form triblock or pentablock copolymers. If the blocks are sufficiently incompatible and the copolymer behaves as a thermoplastic elastomer, the molecules can spontaneously self-assemble to form nanostructured materials that exhibit shape memory due to the formation of a supramolecular network. The BCs of these types are termed as conventional. When BCs contain blocks having ionic moieties such as sulfonic acid groups, they are termed as block ionomers. Designing new systems based on either conventional or ionic BCs, characterizing their structure-property relationships and later using them as electroacive polymers form the essential objectives of this work. Electroactive polymers (EAPs) exhibit electromechanical actuation when stimulated by an external electric field. In the first part of this work, it is shown that BCs resolve some of the outstanding problems presently encountered in the design of two different classes of EAP actuators: dielectric elastomers (DEs) and ionic polymer metal composites (IPMCs). All-acrylic triblock copolymer gels used as DEs actuate with high efficacy without any requirement of mechanical prestrain and, thus, eliminate the need for bulky and heavy hardware essential with prestrained dielectric actuators, as well as material problems associated with stress relaxation. The dependence of actuation behavior on gel morphology as evaluated from mechanical and microstructure studies is observed. In the case of IPMCs, ionic BCs employed in this study greatly facilitate processing compared to other contenders such as NafionRTM, which is commonly used in this class of EAPs. The unique copolymer investigated here (i) retains its mechanical integrity when highly solvated by polar solvents, (ii) demonstrates a high degree of actuation when tested in a cantilever configuration, and (iii) avoids the shortcomings of back-relaxation/overshoot within the testing conditions when used in combination with an appropriate solvent. In the second part of this work, two chemical strategies to design midblock sulfonated block ionomers are explored. In one case, selective sulfonation of the midblocks in triblock copolymers is achieved via a dioxane:sulfur trioxide chemistry, while in the other acetyl sulfate is used for the same purpose. Excellent control on the degree of sulfonation (DOS) is achieved. The block ionomers swell in different solvents while retaining their mechanical integrity. They show disorder-order, order-order, and order-reduced order morphological transitions as DOS varies. These transitions in morphologies are reflected in their thermal behavior as well. The microstructures show periodicity, which is, again, a function of DOS. The transitions are explained in terms of the molar volume expansion and volume densification of the blocks on sulfonation. The ionic levels, morphology and periodicity in microstructure are important for applications such as actuators, sensors and fuel cell membranes. The ability to tune these aspects in the ionomers designed in this work make them potential candidates for these applications.

Ceramic matrix and resin matrix composites: A comparison

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.

1987-01-01

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Ceramic matrix and resin matrix composites - A comparison

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.

1987-01-01

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Microstructural aspects in steel fiber reinforced acrylic emulsion polymer modified concrete

NASA Astrophysics Data System (ADS)

Hazimmah, Dayang; Ayob, Afizah; Sie Yee, Lau; Chee Cung, Wong

2018-03-01

Scanning electron microscope observations of polymer-free and polymer-modified cements have shown that the polymer particles are partitioned between the inside of hydrates and the surface of anhydrous cement grains. For optimum dosage of acrylic emulsion polymer with 2.5%, the C-S-H gel in this structure is finer and more acicular. Some polymer adheres or deposit on the surface of the C-S-H gel. The presence of acrylic emulsion polymer confines the ionic diffusion so that the Ca(OH)2 crystallized locally to form fine crystals. The void in the structures seems to be smaller but no polymer films appears to be bridging the walls of pores although many polymer bonds or C-S-H spread into the pore spaces. In addition to porosity reduction, acrylic emulsion polymer modified the hydration products in the steel fiber -matrix ITZ. The hydration product C-S-H appeared as a needle like shape. The needle-shaped C-S-H increases and gradually formed the gel, with needles growing into the pore space. The phenomenon is more obvious as curing age increased.

Resistive switching characteristics of polymer non-volatile memory devices in a scalable via-hole structure.

PubMed

Kim, Tae-Wook; Choi, Hyejung; Oh, Seung-Hwan; Jo, Minseok; Wang, Gunuk; Cho, Byungjin; Kim, Dong-Yu; Hwang, Hyunsang; Lee, Takhee

2009-01-14

The resistive switching characteristics of polyfluorene-derivative polymer material in a sub-micron scale via-hole device structure were investigated. The scalable via-hole sub-microstructure was fabricated using an e-beam lithographic technique. The polymer non-volatile memory devices varied in size from 40 x 40 microm(2) to 200 x 200 nm(2). From the scaling of junction size, the memory mechanism can be attributed to the space-charge-limited current with filamentary conduction. Sub-micron scale polymer memory devices showed excellent resistive switching behaviours such as a large ON/OFF ratio (I(ON)/I(OFF) approximately 10(4)), excellent device-to-device switching uniformity, good sweep endurance, and good retention times (more than 10,000 s). The successful operation of sub-micron scale memory devices of our polyfluorene-derivative polymer shows promise to fabricate high-density polymer memory devices.

Space charge effects on the dielectric response of polymer nanocomposites

NASA Astrophysics Data System (ADS)

Shen, Zhong-Hui; Wang, Jian-Jun; Zhang, Xin; Lin, Yuanhua; Nan, Ce-Wen; Chen, Long-Qing; Shen, Yang

2017-08-01

Adding high-κ ceramic nanoparticles into polymers is a general strategy to improve the performances in energy storage. Classic effective medium theories may fail to predict the effective permittivity in polymer nanocomposites wherein the space charge effects are important. In this work, a computational model is developed to understand the space charge effects on the frequency-dependent dielectric properties including the real permittivity and the loss for polymer nanocomposites with both randomly distributed and aggregated nanoparticle fillers. It is found that the real permittivity of the SrTiO3/polyethylene (12% SrTiO3 in volume fraction) nanocomposite can be increased to as high as 60 when there is nanoparticle aggregation and the ion concentration in the bulk polymer is around 1016 cm-3. This model can be employed to quantitatively predict the frequency-dependent dielectric properties for polymer nanocomposites with arbitrary microstructures.

A novel liquid-filled microstructured polymer optical fiber as bio-sensing platform for Raman spectroscopy

NASA Astrophysics Data System (ADS)

Azkune, Mikel; Arrospide, Eneko; Berganza, Amaia; Bikandi, Iñaki; Aldabaldetreku, Gotzon; Durana, Gaizka; Zubia, Joseba

2018-02-01

One approach to overcome the poor efficiency of the Raman scattering as a sensing platform is to use microstructured optical fibers. In this type of fibers with a longitudinal holey structure, light interacts with the target sample, which is confined in the core, giving rise to a light intensity increase of the obtained Raman spectra due to the large interaction distances and the guidance of the scattered light. In this work, we present an ad-hoc fabricated liquid-core microstructured polymer optical fiber (LC-mPOF) as a bio-sensing platform for Raman Spectroscopy. Arising from an initial simulation stage, we create the desired preform using the drilling technique and afterwards the LC-mPOF is drawn in our fiber drawing tower. The guiding mechanism of the light through the solution has a major importance, being a key factor to obtain appreciable enhancements in Raman scattering. In this case, in order to optimize the Raman scattering signal of dissolved glucose (target molecule), we have filled the core with an aqueous solution of the target molecule, enabling in this way the modified total internal reflection mechanism. Experimental Raman measurements are performed and results are discussed.

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization and microstructure of HPMC/Gly:AgNO3 polymer composites

NASA Astrophysics Data System (ADS)

Ananda, H. T.; Urs, G. Thejas; Somashekar, R.

2018-04-01

This study reports the synthesis and characterization of AgNo3 doped HPMC/Glycerol blend films. The microstructural parameters of these composites were evaluated employing whole powder pattern fitting method (WPPF) and the results obtained are related with other physical properties. AC conductivity results and optical band gap evaluated from UV/Vis studies are focused to establish structure property relations. These composite films are bio-degradable in nature and non-hazardous, this makes them very suitable candidates for applications in appropriate fields.

Characterising the structural properties of polymer separators for lithium-ion batteries in 3D using phase contrast X-ray microscopy

NASA Astrophysics Data System (ADS)

Finegan, Donal P.; Cooper, Samuel J.; Tjaden, Bernhard; Taiwo, Oluwadamilola O.; Gelb, Jeff; Hinds, Gareth; Brett, Dan J. L.; Shearing, Paul R.

2016-11-01

Separators are an integral component for optimising performance and safety of lithium-ion batteries; therefore, a clear understanding of how their microstructure affects cell performance and safety is crucial. Phase contrast X-ray microscopy is used here to capture the microstructures of commercial monolayer, tri-layer, and ceramic-coated lithium-ion battery polymer separators. Spatial variations in key structural parameters, including porosity, tortuosity factor and pore size distribution, are determined through the application of 3D quantification techniques and stereology. The architectures of individual layers in multi-layer membranes are characterised, revealing anisotropy in porosity, tortuosity factor and mean pore size of the three types of separator. Detailed structural properties of the individual layers of multi-layered membranes are then related with their expected effect on safety and rate capability of cells.

Dependence of triboelectric charging behavior on material microstructure

NASA Astrophysics Data System (ADS)

Wang, Andrew E.; Gil, Phwey S.; Holonga, Moses; Yavuz, Zelal; Baytekin, H. Tarik; Sankaran, R. Mohan; Lacks, Daniel J.

2017-08-01

We demonstrate that differences in the microstructure of chemically identical materials can lead to distinct triboelectric charging behavior. Contact charging experiments are carried out between strained and unstrained polytetrafluoroethylene samples. Whereas charge transfer is random between samples of identical strain, when one of the samples is strained, systematic charge transfer occurs. No significant changes in the molecular-level structure of the polymer are observed by XRD and micro-Raman spectroscopy after deformation. However, the strained surfaces are found to exhibit void and craze formation spanning the nano- to micrometer length scales by molecular dynamics simulations, SEM, UV-vis spectroscopy, and naked-eye observations. This suggests that material microstructure (voids and crazes) can govern the triboelectric charging behavior of materials.

Synthetic principles directing charge transport in low-band-gap dithienosilole-benzothiadiazole copolymers.

PubMed

Beaujuge, Pierre M; Tsao, Hoi Nok; Hansen, Michael Ryan; Amb, Chad M; Risko, Chad; Subbiah, Jegadesan; Choudhury, Kaushik Roy; Mavrinskiy, Alexei; Pisula, Wojciech; Brédas, Jean-Luc; So, Franky; Müllen, Klaus; Reynolds, John R

2012-05-30

Given the fundamental differences in carrier generation and device operation in organic thin-film transistors (OTFTs) and organic photovoltaic (OPV) devices, the material design principles to apply may be expected to differ. In this respect, designing organic semiconductors that perform effectively in multiple device configurations remains a challenge. Following "donor-acceptor" principles, we designed and synthesized an analogous series of solution-processable π-conjugated polymers that combine the electron-rich dithienosilole (DTS) moiety, unsubstituted thiophene spacers, and the electron-deficient core 2,1,3-benzothiadiazole (BTD). Insights into backbone geometry and wave function delocalization as a function of molecular structure are provided by density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level. Using a combination of X-ray techniques (2D-WAXS and XRD) supported by solid-state NMR (SS-NMR) and atomic force microscopy (AFM), we demonstrate fundamental correlations between the polymer repeat-unit structure, molecular weight distribution, nature of the solubilizing side-chains appended to the backbones, and extent of structural order attainable in p-channel OTFTs. In particular, it is shown that the degree of microstructural order achievable in the self-assembled organic semiconductors increases largely with (i) increasing molecular weight and (ii) appropriate solubilizing-group substitution. The corresponding field-effect hole mobilities are enhanced by several orders of magnitude, reaching up to 0.1 cm(2) V(-1) s(-1) with the highest molecular weight fraction of the branched alkyl-substituted polymer derivative in this series. This trend is reflected in conventional bulk-heterojunction OPV devices using PC(71)BM, whereby the active layers exhibit space-charge-limited (SCL) hole mobilities approaching 10(-3) cm(2) V(-1) s(-1), and yield improved power conversion efficiencies on the order of 4.6% under AM1.5G solar illumination. Beyond structure-performance correlations, we observe a large dependence of the ionization potentials of the polymers estimated by electrochemical methods on polymer packing, and expect that these empirical results may have important consequences on future material study and device applications.

Stablization of Nanotwinned Microstructures in Stainless Steels Through Alloying and Microstructural Design

DTIC Science & Technology

2013-08-23

REPORT Stablization of Nanotwinned Microstructures in Stainless Steels Through Alloying and Microstructural Design 14. ABSTRACT 16. SECURITY...15. SUBJECT TERMS materials design, stainless steels , plastic deformation by twinning, computational materials science, experimental characterization...Standard Form 298 (Rev 8/98) Prescribed by ANSI Std. Z39.18 - 30-Jun-2013 Stablization of Nanotwinned Microstructures in Stainless Steels Through

Wet self-cleaning of superhydrophobic microfiber adhesives formed from high density polyethylene.

PubMed

Lee, Jongho; Fearing, Ronald S

2012-10-30

Biologically inspired adhesives developed for switchable and controllable adhesion often require repetitive uses in general, dirty, environments. Superhydrophobic microstructures on the lotus leaf lead to exceptional self-cleaning of dirt particles on nonadhesive surfaces with water droplets. This paper describes the self-cleaning properties of a hard-polymer-based adhesive formed with high-aspect-ratio microfibers from high-density polyethylene (HDPE). The microfiber adhesive shows almost complete wet self-cleaning of dirt particles with water droplets, recovering 98% of the adhesion of the pristine microfiber adhesives. The low contact angle hysteresis indicates that the surface of microfiber adhesives is superhydrophobic. Theoretical and experimental studies reveal a design parameter, length, which can control the adhesion without affecting the superhydrophobicity. The results suggest some properties of biologically inspired adhesives can be controlled independently by adjusting design parameters.

Physics of the gut: How polymers dynamically structure the gut environment

NASA Astrophysics Data System (ADS)

Preska Steinberg, Asher; Datta, Sujit; Bogatyrev, Said; Ismagilov, Rustem

While the gut microbiome and biological regulation of the gut environment is being exhaustively studied by the microbiology community, little is known about the rich physics that governs the macro- and microstructure of the gut environment. The mammalian gut abounds in soft materials; ranging from soluble polymers (e.g. dietary fibers, therapeutic polymers and mucins) to colloidal matter (e.g. bacteria, viruses and nanoparticles carrying drugs). We have found experimentally that soluble polymers can dynamically re-structure the colonic mucus hydrogel by modulating its degree of swelling. We implemented a mean-field Flory-Huggins model to reveal that these polymer-mucus interactions can be captured using a simple, first principles thermodynamics model. In this model, the amount of deswelling increases with polymer concentration and size. We then used these physical principles to make predictions about how different polymer solutions affect the structure of mucus. Lastly, we explore applying this framework and similar physical principles to a variety of biological problems in the gut.

The effect of water-soluble polymers on the microstructure and properties of freeze-cast alumina ceramics

NASA Astrophysics Data System (ADS)

Pekor, Christopher Michael

Porous ceramics can be divided into three separate classes based on their pore size: microporous ceramics with pores less than 2 nm, mesoporous ceramics with pores in the range of 2--50 nm and macroporous ceramics with pores that are greater than 50 nm. In particular, macroporous ceramics are used in a variety of applications such as refractories, molten metal filtration, diesel particulate filters, heterogeneous catalyst supports and biomedical scaffolds. Freeze casting is a novel method used to create macroporous ceramics. In this method growing ice crystals act as a template for the pores and are solidified, often directionally, through a ceramic dispersion and removed from the green body through a freeze drying procedure. This method has attracted some attention over the past few years due to its relative simplicity, flexibility and environmental friendliness. On top of this freeze casting is capable of producing materials with high pore volume fractions, which is an advantage over processing by packing and necking of particles, where the pore volume fraction is typically less than 50%. Many of the basic processing variables that affect the freeze cast microstructure, such as the temperature gradient, interfacial velocity and solid loading of the dispersion have been well established in the literature. On the other hand, areas such as the effect of additives on the microstructure and mechanical properties have not been covered in great detail. In this study the concept of constitutional supercooling from basic solidification theory is used to explain the effects of two water-soluble polymers, polyethylene glycol and polyvinyl alcohol, on the microstructure of freeze cast alumina ceramics. In addition, changes in the observed microstructure will be related to experimentally determined values of permeability and compressive strength.

Microstructural characterization of PAN based carbon fiber reinforced nylon 6 polymer composites

NASA Astrophysics Data System (ADS)

Munirathnamma, L. M.; Ningaraju, S.; Kumar, K. V. Aneesh; Ravikumar, H. B.

2018-04-01

Microstructural characterization of nylon 6/polyacrolonitrile based carbon fibers (PAN-CFs) of 10 to 40 wt% has been performed by positron lifetime technique (PLT). The positron lifetime parameters viz., o-Ps lifetime (τ3), o-Ps intensity (I3) and fractional free volume (Fv) of nylon 6/PAN-CF composites are correlated with the mechanical properties viz., Tensile strength and Young's modulus. The Fv show negative deviation with the reinforcement of 10 to 40 wt% of PAN-CF from the linear additivity relation. The negative deviation in nylon 6/PAN-CF composite suggests the induced molecular packing due to the chemical interaction between the polymeric chains of nylon 6 and PAN-CF. This is evident from Fourier Transform Infrared Spectrometry (FTIR) studies. The FTIR results suggests that observed negative deviation in PALS results of nylon 6/PAN-CF reinforced polymer composites is due to the induced chemical interaction at N-H-O sites. The improved tensile strength (TS) and Young's modulus (YM) in nylon 6/PAN-CF reinforced polymer composites is due to AS4C (surface treated and epoxy coated) PAN-CF has shown highest adhesion level due to better stress transfer between nylon 6 and PAN-CF.

Topographic measurement of buried thin-film interfaces using a grazing resonant soft x-ray scattering technique

NASA Astrophysics Data System (ADS)

Gann, Eliot; Watson, Anne; Tumbleston, John R.; Cochran, Justin; Yan, Hongping; Wang, Cheng; Seok, Jaewook; Chabinyc, Michael; Ade, Harald

2014-12-01

The internal structures of thin films, particularly interfaces between different materials, are critical to system properties and performance across many disciplines, but characterization of buried interface topography is often unfeasible. In this work, we demonstrate that grazing resonant soft x-ray scattering (GRSoXS), a technique measuring diffusely scattered soft x rays from grazing incidence, can reveal the statistical topography of buried thin-film interfaces. By controlling and predicting the x-ray electric field intensity throughout the depth of the film and simultaneously the scattering contrast between materials, we are able to unambiguously identify the microstructure at different interfaces of a model polymer bilayer system. We additionally demonstrate the use of GRSoXS to selectively measure the topography of the surface and buried polymer-polymer interface in an organic thin-film transistor, revealing different microstructure and markedly differing evolution upon annealing. In such systems, where only indirect control of interface topography is possible, accurate measurement of the structure of interfaces for feedback is critically important. While we demonstrate the method here using organic materials, we also show that the technique is readily extendable to any thin-film system with elemental or chemical contrasts exploitable at absorption edges.

Microfluidic active mixers employing ultra-high aspect-ratio rare-earth magnetic nano-composite polymer artificial cilia

NASA Astrophysics Data System (ADS)

Rahbar, Mona; Shannon, Lesley; Gray, Bonnie L.

2014-02-01

We present a new micromixer based on highly magnetic, flexible, high aspect-ratio, artificial cilia that are fabricated as individual micromixer elements or in arrays for improved mixing performance. These new cilia enable high efficiency, fast mixing in a microchamber, and are controlled by small electromagnetic fields. The artificial cilia are fabricated using a new micromolding process for nano-composite polymers. Cilia fibers with aspect-ratios as high as 8:0.13 demonstrate the fabrication technique's capability in creating ultra-high aspect-ratio microstructures. Cilia, which are realized in polydimethylsiloxane doped with rare-earth magnetic powder, are magnetized to produce permanent magnetic structures with bidirectional deflection capabilities, making them highly suitable as mixers controlled by electromagnetic fields. Due to the high magnetization level of the polarized nano-composite polymer, we are able to use miniature electromagnets providing relatively small magnetic fields of 1.1 to 7 mT to actuate the cilia microstructures over a very wide motion range. Mixing performances of a single cilium, as well as different arrays of multiple cilia ranging from 2 to 8 per reaction chamber, are characterized and compared with passive diffusion mixing performance. The mixer cilia are actuated at different amplitudes and frequencies to optimize mixing performance. We demonstrate that more than 85% of the total volume of the reaction chamber is fully mixed after 3.5 min using a single cilium mixer at 7 mT compared with only 20% of the total volume mixed with passive diffusion. The time to achieve over 85% mixing is further reduced to 70 s using an array of eight cilia microstructures. The novel microfabrication technique and use of rare-earth permanently-magnetizable nano-composite polymers in mixer applications has not been reported elsewhere by other researchers. We further demonstrate improved mixing over other cilia micromixers as enabled by the high aspect-ratio, high flexibility, and magnetic properties of our cilia micromixer elements.

Rapid bio-patterning method based on the fabrication of PEG microstructures and layer-by-layer polymeric thin film

NASA Astrophysics Data System (ADS)

Shim, Hyun-Woo; Lee, Ji-Hye; Choi, Chang-Hyoung; Song, Hwan-Moon; Kim, Bo-Yeol; Kim, Dong-Pyo; Lee, Chang-Soo

2007-12-01

The patterning of biomolecules in well-defined microstructures is critical issue for the development of biosensors and biochips. However, the fabrication of microstructures with well-ordered and spatially discrete forms to provide the patterned surface for the immobilization of biomolecules is difficult because of the lack of distinct physical and chemical barriers separating patterns. This study present rapid biomolecule patterning using micromolding in capillaries (MIMIC), soft-lithographic fabrication of PEG microstructures for prevention of nonspecific binding as a biological barrier, and self assembled polymeric thin film for efficient immobilization of proteins or cells. For the proof of concept, protein (FITC-BSA), bacteria (E.coli BL21-pET23b-GFP) were used for biomolecules patterning on polyelectrolyte coated surface within PEG microstructures. The novel approach of MIMIC combined with LbL coating provides a general platform for patterning a broad range of materials because it can be easily applied to various substrates such as glass, silicon, silicon dioxide, and polymers.

Maleic anhydride-g-low density polyethylene: Modification of LDPE molecular structure by γ-irradiation

NASA Astrophysics Data System (ADS)

Sheeja, Manaf, O.; Sujith, A.

2017-06-01

Polymer modification by radiation grafting of monomers onto polymers has received much attention recently. In the current study, γ-irradiation technique was used to achieve graft copolymerization of maleic anhydride (MA) onto low-density polyethylene (LDPE). To optimize, the process was performed at different γ-irradiation doses and MA concentration. The microstructure of grafted polymer film has been characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, field emission-scanning electron microscopy, and atomic force microscopy. The studies performed made possible the selection of experimental protocols adequate for the production of new copolymeric materials with high grafting yield.

Phase transitions and structural formation of PEG-PCL-PEG copolymer in the processes of fused deposition 3D printing

NASA Astrophysics Data System (ADS)

Dunaev, A.; Mariyanac, A.; Mironov, A.; Mironova, O.; Popov, V.; Syachina, M.

2018-04-01

In present work the analysis of thermal field distribution and thermal analysis were used to study phase and structural transformations in the block copolymer of polycaprolactone and polyethylene glycol in the process of scaffolds fabrication for tissue engineering using fused deposition modeling. It was shown that the intact polymer has a noticeable thermal history and formed degree of crystallinity which is close to its equilibrium value, while the microstructure of the polymer stays unchanged.

Recent Development of Thermoelectric Polymers and Composites.

PubMed

Yao, Hongyan; Fan, Zeng; Cheng, Hanlin; Guan, Xin; Wang, Chen; Sun, Kuan; Ouyang, Jianyong

2018-03-01

Thermoelectric materials can be used as the active materials in thermoelectric generators and as Peltier coolers for direct energy conversion between heat and electricity. Apart from inorganic thermoelectric materials, thermoelectric polymers have been receiving great attention due to their unique advantages including low cost, high mechanical flexibility, light weight, low or no toxicity, and intrinsically low thermal conductivity. The power factor of thermoelectric polymers has been continuously rising, and the highest ZT value is more than 0.25 at room temperature. The power factor can be further improved by forming composites with nanomaterials. This article provides a review of recent developments on thermoelectric polymers and polymer composites. It focuses on the relationship between thermoelectric properties and the materials structure, including chemical structure, microstructure, dopants, and doping levels. Their thermoelectric properties can be further improved to be comparable to inorganic counterparts in the near future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saha, Sourabh K.; Oakdale, James S.; Cuadra, Jefferson A.

Two-photon lithography (TPL) is a high-resolution additive manufacturing (AM) technique capable of producing arbitrarily complex three-dimensional (3D) microstructures with features 2–3 orders of magnitude finer than human hair. This process finds numerous applications as a direct route toward the fabrication of novel optical and mechanical metamaterials, miniaturized optics, microfluidics, biological scaffolds, and various other intricate 3D parts. As TPL matures, metrology and inspection become a crucial step in the manufacturing process to ensure that the geometric form of the end product meets design specifications. X-ray-based computed tomography (CT) is a nondestructive technique that can provide this inspection capability for themore » evaluation of complex internal 3D structure. However, polymeric photoresists commonly used for TPL, as well as other forms of stereolithography, poorly attenuate X-rays due to the low atomic number (Z) of their constituent elements and therefore appear relatively transparent during imaging. We present the development of optically clear yet radiopaque photoresists for enhanced contrast under X-ray CT. We have synthesized iodinated acrylate monomers to formulate high-Z photoresist materials that are capable of forming 3D microstructures with sub-150 nm features. In addition, we have developed a formulation protocol to match the refractive index of the photoresists to the immersion medium of the objective lens so as to enable dip-in laser lithography, a direct laser writing technique for producing millimeter-tall structures. Our radiopaque photopolymer then resists increase X-ray attenuation by a factor of more than 10 times without sacrificing the sub-150 nm feature resolution or the millimeter-scale part height. Thus, our resists can successfully replace existing photopolymers to generate AM parts that are suitable for inspection via X-ray CT. By providing the “feedstock” for radiopaque AM parts, our resist formulation is expected to play a critical role in enabling fabrication of functional polymer parts to tight design tolerances.« less

Radiopaque Resists for Two-Photon Lithography To Enable Submicron 3D Imaging of Polymer Parts via X-ray Computed Tomography

DOE PAGES

Saha, Sourabh K.; Oakdale, James S.; Cuadra, Jefferson A.; ...

2017-11-24

Two-photon lithography (TPL) is a high-resolution additive manufacturing (AM) technique capable of producing arbitrarily complex three-dimensional (3D) microstructures with features 2–3 orders of magnitude finer than human hair. This process finds numerous applications as a direct route toward the fabrication of novel optical and mechanical metamaterials, miniaturized optics, microfluidics, biological scaffolds, and various other intricate 3D parts. As TPL matures, metrology and inspection become a crucial step in the manufacturing process to ensure that the geometric form of the end product meets design specifications. X-ray-based computed tomography (CT) is a nondestructive technique that can provide this inspection capability for themore » evaluation of complex internal 3D structure. However, polymeric photoresists commonly used for TPL, as well as other forms of stereolithography, poorly attenuate X-rays due to the low atomic number (Z) of their constituent elements and therefore appear relatively transparent during imaging. We present the development of optically clear yet radiopaque photoresists for enhanced contrast under X-ray CT. We have synthesized iodinated acrylate monomers to formulate high-Z photoresist materials that are capable of forming 3D microstructures with sub-150 nm features. In addition, we have developed a formulation protocol to match the refractive index of the photoresists to the immersion medium of the objective lens so as to enable dip-in laser lithography, a direct laser writing technique for producing millimeter-tall structures. Our radiopaque photopolymer then resists increase X-ray attenuation by a factor of more than 10 times without sacrificing the sub-150 nm feature resolution or the millimeter-scale part height. Thus, our resists can successfully replace existing photopolymers to generate AM parts that are suitable for inspection via X-ray CT. By providing the “feedstock” for radiopaque AM parts, our resist formulation is expected to play a critical role in enabling fabrication of functional polymer parts to tight design tolerances.« less

Biomimetic Materials by Freeze Casting

NASA Astrophysics Data System (ADS)

Porter, Michael M.; Mckittrick, Joanna; Meyers, Marc A.

2013-06-01

Natural materials, such as bone and abalone nacre, exhibit exceptional mechanical properties, a product of their intricate microstructural organization. Freeze casting is a relatively simple, inexpensive, and adaptable materials processing method to form porous ceramic scaffolds with controllable microstructural features. After infiltration of a second polymeric phase, hybrid ceramic-polymer composites can be fabricated that closely resemble the architecture and mechanical performance of natural bone and nacre. Inspired by the narwhal tusk, magnetic fields applied during freeze casting can be used to further control architectural alignment, resulting in freeze-cast materials with enhanced mechanical properties.

Role of succinonitrile in improving ionic conductivity of sodium-ion conductive polymer electrolyte

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Mohapatra, Saumya R.

2018-05-01

Sodium ion conducting solid polymer electrolytes were prepared using poly (ethylene oxide) (PEO) as polymer matrix, sodium perchlorate (NaClO4) as salt and succinonitrile (SN) as a plasticizer by solution casting technique. By blending a plastic crystal such as succinonitrile (SN) with PEO-NaClO4 electrolyte system, we aimed at improving the ionic conductivity by weakening the ether oxygen-Na+ interactions. The XRD and FTIR studies revealed structural and micro-structural changes in the blended electrolytes which aids in improving ionic conductivity. Also, DSC measurements showed improved segmental motion in the blended polymer electrolytes due to plasticizing effect of SN. The maximum ionic conductivity observed at room temperature is 1.13×10-5 S cm-1 merely for 7 wt. % of SN, which is one order higher than pure polymer-salt complex. The thermo-gravimetric analysis (TGA) suggests that blending of SN with polymer electrolyte had no detrimental effect on its thermal stability.

Integrated circuits based on conjugated polymer monolayer

DOE PAGES

Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo; ...

2018-01-31

It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2 V -1 s -1. The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Realmore » logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Lastly, our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.« less

Integrated circuits based on conjugated polymer monolayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo

It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2 V -1 s -1. The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Realmore » logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Lastly, our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.« less

Integrated circuits based on conjugated polymer monolayer.

PubMed

Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo; Carpenter, Joshua H; Yan, Hongping; Ade, Harald; Yan, He; Müllen, Klaus; Blom, Paul W M; Pisula, Wojciech; de Leeuw, Dago M; Asadi, Kamal

2018-01-31

It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2  V -1  s -1 . The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.

The influence of TiO2 composition in LiBOB electrolyte polymer composite membrane characteristics for lithium ion batteries applications

NASA Astrophysics Data System (ADS)

Lestariningsih, T.; Sabrina, Q.; Wigayati, E. M.

2018-03-01

Characterization of the composite membrane of LiBOB electrolyte polymers made from poly (vinylidene fluoride co-hexafluororopylene) (PVdF-HFP) as the polymer, LiBOB or LiB(C2O4)2 as electrolyte salt and titanium dioxide (TiO2) as ceramic filler of three different concentrations have been done. Sample of membrane was prepared using solution casting technique. Microstructural study by SEM shows non-uniform distribution of pore over the surface of the sample. X-ray structural analysis, impedance spectroscopy, and cyclic voltammetry (CV) studies were carried out. Membrane composite polymer of LiBOB electrolyte without additional ceramic filler with composition of 70% polymer, 30% LiBOB, and 0% TiO2 has the greatest conductivity for forming amorphous phase and is compatible with material membrane composite. Meanwhile, sample with 70% polymer composition, 28% LiBOB and 2% TiO2 shows oxidation reaction at the most perfect discharge despite very slow current speed.

Microstructure and Properties of Polypropylene/Carbon Nanotube Nanocomposites

PubMed Central

Bikiaris, Dimitrios

2010-01-01

In the last few years, great attention has been paid to the preparation of polypropylene (PP) nanocomposites using carbon nanotubes (CNTs) due to the tremendous enhancement of the mechanical, thermal, electrical, optical and structural properties of the pristine material. This is due to the unique combination of structural, mechanical, electrical, and thermal transport properties of CNTs. However, it is well-known that the properties of polymer-based nanocomposites strongly depend on the dispersion of nanofillers and almost all the discussed properties of PP/CNTs nanocomposites are strongly related to their microstructure. PP/CNTs nanocomposites were, mainly, prepared by melt mixing and in situ polymerization. Young’s modulus, tensile strength and storage modulus of the PP/CNTs nanocomposites can be increased with increasing CNTs content due to the reinforcement effect of CNTs inside the polymer matrix. However, above a certain CNTs content the mechanical properties are reduced due to the CNTs agglomeration. The microstructure of nanocomposites has been studied mainly by SEM and TEM techniques. Furthermore, it was found that CNTs can act as nucleating agents promoting the crystallization rates of PP and the addition of CNTs enhances all other physical properties of PP. The aim of this paper is to provide a comprehensive review of the existing literature related to PP/CNTs nanocomposite preparation methods and properties studies.

Dental ceramics: a review of new materials and processing methods.

PubMed

Silva, Lucas Hian da; Lima, Erick de; Miranda, Ranulfo Benedito de Paula; Favero, Stéphanie Soares; Lohbauer, Ulrich; Cesar, Paulo Francisco

2017-08-28

The evolution of computerized systems for the production of dental restorations associated to the development of novel microstructures for ceramic materials has caused an important change in the clinical workflow for dentists and technicians, as well as in the treatment options offered to patients. New microstructures have also been developed by the industry in order to offer ceramic and composite materials with optimized properties, i.e., good mechanical properties, appropriate wear behavior and acceptable aesthetic characteristics. The objective of this literature review is to discuss the main advantages and disadvantages of the new ceramic systems and processing methods. The manuscript is divided in five parts: I) monolithic zirconia restorations; II) multilayered dental prostheses; III) new glass-ceramics; IV) polymer infiltrated ceramics; and V) novel processing technologies. Dental ceramics and processing technologies have evolved significantly in the past ten years, with most of the evolution being related to new microstructures and CAD-CAM methods. In addition, a trend towards the use of monolithic restorations has changed the way clinicians produce all-ceramic dental prostheses, since the more aesthetic multilayered restorations unfortunately are more prone to chipping or delamination. Composite materials processed via CAD-CAM have become an interesting option, as they have intermediate properties between ceramics and polymers and are more easily milled and polished.

Morphology, microstructure, and magnetic properties of ordered large-pore mesoporous cadmium ferrite thin film spin glasses.

PubMed

Reitz, Christian; Suchomski, Christian; Chakravadhanula, Venkata Sai Kiran; Djerdj, Igor; Jagličić, Zvonko; Brezesinski, Torsten

2013-04-01

Herein, we report the synthesis, microstructure, and magnetic properties of cadmium ferrite (CdFe2O4) thin films with both an ordered cubic network of 18 nm diameter pores and single-phase spinel grains averaging 13 nm in diameter. These mesoporous materials were produced through facile polymer templating of hydrated nitrate salt precursors. Both the morphology and the microstructure, including cation site occupancy and electronic bonding configuration, were analyzed in detail by electron microscopy, grazing incidence small-angle X-ray scattering, Raman and X-ray photoelectron spectroscopy, and N2-physisorption. The obtained data demonstrate that the network of pores is retained up to annealing temperatures as high as 650 °C--the onset of crystallization is at ϑ = (590 ± 10) °C. Furthermore, they show that the polymer-templated samples exhibit a "partially" inverted spinel structure with inversion parameter λ = 0.40 ± 0.02. This differs from microcrystalline CdFe2O4 which shows virtually no inversion. Magnetic susceptibility studies reveal ferrimagnetic spin coupling below 147 K and further point to the likelihood of glassy behavior at low temperature (T(f) ≈ 60 K). In addition, analysis of room temperature magnetization data indicates the presence of sub-10 nm diameter superparamagnetic clusters in an otherwise paramagnetic environment.

Enabling high-precision nonlinear three-dimensional photoprocessing of premeditated designs on a conventional multiphoton imaging system

NASA Astrophysics Data System (ADS)

Garsha, Karl E.

2004-06-01

There is an increasing amount of interest in functionalized microstructural, microphotonic and microelectromechanical systems (MEMS) for use in biological applications. By scanning a tightly focused ultra-short pulsed laser beam inside a wide variety of commercially available polymer systems, the flexibility of the multiphoton microscope can be extended to include routine manufacturing of micro-devices with feature sizes well below the diffraction limit. Compared with lithography, two-photon polymerization has the unique ability to additively realize designs with high resolution in three dimensions; this permits the construction of cross-linked components and structures with hollow cavities. In light of the increasing availability of multiphoton imaging systems at research facilities, femtosecond laser manufacturing becomes particularly attractive in that the modality provides a readily accessible, rapid and high-accuracy 3-D processing capability to biological investigators interested in culture scaffolds and biomimetic tissue engineering, bio-MEMS, biomicrophotonics and microfluidics applications. This manuscript overviews recent efforts towards to enabling user accessible 3-D micro-manufacturing capabilities on a conventional proprietary-based imaging system. Software which permits the off-line design of microstructures and leverages the extensibility of proprietary LCSM image acquisition software to realize designs is introduced. The requirements for multiphoton photo-disruption (ablation) are in some ways analogous to those for multiphoton polymerization. Hence, "beam-steering" also facilitates precision photo-disruption of biological tissues with 3-D resolution, and applications involving tissue microdissection and intracellular microsurgery or three-dimensionally resolved fluorescence recovery after photobleaching (FRAP) studies can benefit from this work as well.

Molecular modeling the microstructure and phase behavior of bulk and inhomogeneous complex fluids

NASA Astrophysics Data System (ADS)

Bymaster, Adam

Accurate prediction of the thermodynamics and microstructure of complex fluids is contingent upon a model's ability to capture the molecular architecture and the specific intermolecular and intramolecular interactions that govern fluid behavior. This dissertation makes key contributions to improving the understanding and molecular modeling of complex bulk and inhomogeneous fluids, with an emphasis on associating and macromolecular molecules (water, hydrocarbons, polymers, surfactants, and colloids). Such developments apply broadly to fields ranging from biology and medicine, to high performance soft materials and energy. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's thermodynamic perturbation theory (TPT1), is extended to include a crossover correction that significantly improves the predicted phase behavior in the critical region. In addition, PC-SAFT is used to investigate the vapor-liquid equilibrium of sour gas mixtures, to improve the understanding of mercaptan/sulfide removal via gas treating. For inhomogeneous fluids, a density functional theory (DFT) based on TPT1 is extended to problems that exhibit radially symmetric inhomogeneities. First, the influence of model solutes on the structure and interfacial properties of water are investigated. The DFT successfully describes the hydrophobic phenomena on microscopic and macroscopic length scales, capturing structural changes as a function of solute size and temperature. The DFT is used to investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. A comprehensive study is conducted characterizing the role of polymer concentration and particle/polymer size ratio on the structure, polymer induced depletion forces, and tendency towards colloidal aggregation. The inhomogeneous form of the association functional is used, for the first time, to extend the DFT to associating polymer systems, applicable to any association scheme. Theoretical results elucidate how reversible bonding governs the structure of a fluid near a surface and in confined environments, the molecular connectivity (formation of supramolecules, star polymers, etc.) and the phase behavior of the system. Finally, the DFT is extended to predict the inter- and intramolecular correlation functions of polymeric fluids. A theory capable of providing such local structure is important to understanding how local chemistry, branching, and bond flexibility affect the thermodynamic properties of polymers.

Reactive processing and mechanical properties of polymer derived silicon nitride matrix composites and their use in coating and joining ceramics and ceramic matrix composites

NASA Astrophysics Data System (ADS)

Stackpoole, Margaret Mary

Use of preceramic polymers offers many advantages over conventional ceramic processing routes. Advantages include being able to plastically form the part, form a pyrolized ceramic material at lower temperatures and form high purity microstructures which are tailorable depending on property requirements. To date preceramic polymers are mostly utilized in the production of low dimensional products such as fibers since loss of volatiles during pyrolysis leads to porosity and large shrinkage (in excess of 30%). These problems have been partially solved by use of active fillers (e.g. Ti, Cr, B). The reactive filler converts to a ceramic material with a volume expansion and this increases the density and reduces shrinkage and porosity. The expansion of the reactive filler thus compensates for the polymer shrinkage if the appropriate volume fraction of filler is present in a reactive atmosphere (e.g. N2 or NH3). This approach has resulted in structural composites with limited success. The present research investigates the possibility of using filled preceramic polymers to form net shaped ceramic composite materials and to investigate the use of these unique composite materials to join and coat ceramics and ceramic composites. The initial research focused on phase and microstructural development of bulk composites from the filled polymer/ceramic systems. A processing technique was developed to insure consistency between different samples and the most promising filler/polymer choices for this application have been determined. The processing temperatures and atmospheres have also been optimized. The work covers processing and characterization of bulk composites, joints and coatings. With careful control of processing near net shape bulk composites were fabricated. Both ambient and high temperature strength and fracture toughness was obtained for these composite systems. The potential of using reactively filled preceramic polymers to process joints and coatings was also investigated. A critical thickness below which crack free joints/coatings could be processed was determined. Finally, mechanical properties of the joints and coatings at ambient and elevated temperatures (including oxidation studies) have been evaluated. The interfacial fracture behavior of the joints and coatings was also evaluated.

Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport

PubMed Central

Wang, Gang; Huang, Wei; Eastham, Nicholas D.; Fabiano, Simone; Manley, Eric F.; Zeng, Li; Wang, Binghao; Zhang, Xinan; Chen, Zhihua; Li, Ran; Chang, Robert P. H.; Chen, Lin X.; Bedzyk, Michael J.; Melkonyan, Ferdinand S.; Facchetti, Antonio; Marks, Tobin J.

2017-01-01

Shear-printing is a promising processing technique in organic electronics for microstructure/charge transport modification and large-area film fabrication. Nevertheless, the mechanism by which shear-printing can enhance charge transport is not well-understood. In this study, a printing method using natural brushes is adopted as an informative tool to realize direct aggregation control of conjugated polymers and to investigate the interplay between printing parameters, macromolecule backbone alignment and aggregation, and charge transport anisotropy in a conjugated polymer series differing in architecture and electronic structure. This series includes (i) semicrystalline hole-transporting P3HT, (ii) semicrystalline electron-transporting N2200, (iii) low-crystallinity hole-transporting PBDTT-FTTE, and (iv) low-crystallinity conducting PEDOT:PSS. The (semi-)conducting films are characterized by a battery of morphology and microstructure analysis techniques and by charge transport measurements. We report that remarkably enhanced mobilities/conductivities, as high as 5.7×/3.9×, are achieved by controlled growth of nanofibril aggregates and by backbone alignment, with the adjusted R2 (R2adj) correlation between aggregation and charge transport as high as 95%. However, while shear-induced aggregation is important for enhancing charge transport, backbone alignment alone does not guarantee charge transport anisotropy. The correlations between efficient charge transport and aggregation are clearly shown, while mobility and degree of orientation are not always well-correlated. These observations provide insights into macroscopic charge transport mechanisms in conjugated polymers and suggest guidelines for optimization. PMID:29109282

Shear-induced clustering of Brownian colloids in associative polymer networks at moderate Péclet number

NASA Astrophysics Data System (ADS)

Kim, Juntae; Helgeson, Matthew E.

2016-08-01

We investigate shear-induced clustering and its impact on fluid rheology in polymer-colloid mixtures at moderate colloid volume fraction. By employing a thermoresponsive system that forms associative polymer-colloid networks, we present experiments of rheology and flow-induced microstructure on colloid-polymer mixtures in which the relative magnitudes of the time scales associated with relaxation of viscoelasticity and suspension microstructure are widely and controllably varied. In doing so, we explore several limits of relative magnitude of the relevant dimensionless shear rates, the Weissenberg number Wi and the Péclet number Pe. In all of these limits, we find that the fluid exhibits two distinct regimes of shear thinning at relatively low and high shear rates, in which the rheology collapses by scaling with Wi and Pe, respectively. Using three-dimensionally-resolved flow small-angle neutron scattering measurements, we observe clustering of the suspension above a critical shear rate corresponding to Pe ˜0.1 over a wide range of fluid conditions, having anisotropy with projected orientation along both the vorticity and compressional axes of shear. The degree of anisotropy is shown to scale with Pe. From this we formulate an empirical model for the shear stress and viscosity, in which the viscoelastic network stress is augmented by an asymptotic shear thickening contribution due to hydrodynamic clustering. Overall, our results elucidate the significant role of hydrodynamic interactions in contributing to shear-induced clustering of Brownian suspensions in viscoelastic liquids.

Design and fabrication of thin microvascularised polymer matrices inspired from secondary lamellae of fish gills

NASA Astrophysics Data System (ADS)

Kumar, Prasoon; Gandhi, Prasanna S.; Majumder, Mainak

2016-04-01

Gills are one of the most primitive gas, solute exchange organs available in fishes. They facilitate exchange of gases, solutes and ions with a surrounding water medium through their functional unit called secondary lamella. These lamellae through their extraordinary morphometric features and peculiar arrangement in gills, achieve remarkable mass transport properties. Therefore, in the current study, modeling and simulation of convection-diffusion transport through a two dimensional model of secondary lamella and theoretical analysis of morphometric features of fish gills were carried out. Such study suggested an evolutionary conservation of parametric ratios across fishes of different weights. Further, we have also fabricated a thin microvascularised PDMS matrices mimicking secondary lamella by use of micro-technologies like electrospinning. In addition, we have also demonstrated the fluid flow by capillary action through these thin microvascularised PDMS matrices. Eventually, we also illustrated the application of these thin microvascularied PDMS matrices in solute exchange process under capillary flow conditions. Thus, our study suggested that fish gills have optimized parameteric ratios, at multiple length scale, throughout an evolution to achieve an organ with enhanced mass transport capabilities. Thus, these defined parametric ratios could be exploited to design and develop efficient, scaled-up gas/solute exchange microdevices. We also proposed an inexpensive and scalable method of fabrication of thin microvascularised polymer matrices and demonstrated its solute exchange capabilities under capillary flow conditions. Thus, mimicking the microstructures of secondary lamella will enable fabrication of microvascularised thin polymer systems through micro manufacturing technologies for potential applications in filtration, self-healing/cooling materials and bioengineering.

Power of Ultra Performance Liquid Chromatography/Electrospray Ionization-MS Reconstructed Ion Chromatograms in the Characterization of Small Differences in Polymer Microstructure.

PubMed

Epping, Ruben; Panne, Ulrich; Falkenhagen, Jana

2018-03-06

From simple homopolymers to functionalized, 3-dimensional structured copolymers, the complexity of polymeric materials has become more and more sophisticated. With new applications, for instance, in the semiconductor or pharmaceutical industry, the requirements for the characterization have risen with the complexity of the used polymers. For each additional distribution, an additional dimension in analysis is needed. Small, often isomeric heterogeneities in topology or microstructure can usually not be simply separated chromatographically or distinguished by any common detector but affect the properties of materials significantly. For a drug delivery system, for example, the degree of branching and branching distribution is crucial for the formation of micelles. Instead of a complicated, time-consuming, and/or expensive 2D-chromatography or ion mobility spectrometry (IMS) method, that also has its limitations, in this work, a simple approach using size exclusion chromatography (SEC) coupled with electrospray ionization (ESI) mass spectrometry is proposed. The online coupling allows the analysis of reconstructed ion chromatograms (RICs) of each degree of polymerization. While a complete separation often cannot be achieved, the derived retention times and peak widths lead to information on the existence and dispersity of heterogeneities. Although some microstructural heterogeneities like short chain branching can for large polymers be characterized with methods such as light scattering, for oligomers where the heterogeneities just start to form and their influence is at the maximum, they are inaccessible with these methods. It is also shown that with a proper calibration even quantitative information can be obtained. This method is suitable to detect small differences in, e.g., branching, 3D-structure, monomer sequence, or tacticity and could potentially be used in routine analysis to quickly determine deviations.

Formation of a periodic diffractive structure based on poly(methyl methacrylate) with ion-implanted silver nanoparticles

NASA Astrophysics Data System (ADS)

Galyautdinov, M. F.; Nuzhdin, V. I.; Fattakhov, Ya. V.; Farrakhov, B. F.; Valeev, V. F.; Osin, Yu. N.; Stepanov, A. L.

2016-02-01

We propose to form optical diffractive elements on the surface of poly(methyl methacrylate) (PMMA) by implanting the polymer with silver ions ( E = 30 keV; D = 5.0 × 1014 to 1.5 × 1017 ion/cm2; I = 2 μA/cm2) through a nickel grid (mask). Ion implantation leads to the nucleation and growth of silver nanoparticles in unmasked regions of the polymer. The formation of periodic surface microstructures during local sputtering of the polymer by incident ions was monitored using an optical microscope. The diffraction efficiency of obtained gratings is demonstrated under conditions of their probing with semiconductor laser radiation in the visible spectral range.

MESOSCALE MODELING OF DEFLAGRATION-INDUCED DECONSOLIDATION IN POLYMER-BONDED EXPLOSIVES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Springer, H K; Glascoe, E A; Reaugh, J E

Initially undamaged polymer-bonded explosives can transition from conductive burning to more violent convective burning via rapid deconsolidation at higher pressures. The pressure-dependent infiltration of cracks and pores, i.e., damage, by product gases at the burn-front is a key step in the transition to convective burning. However, the relative influence of pre-existing damage and the evolution of deflagration-induced damage during the transition to convective burning is not well understood. The objective of this study is to investigate the role of microstructure and initial pressurization on deconsolidation. We performed simulations using the multi-physics hydrocode, ALE3D. HMX-Viton A served as our model explosive.more » A Prout-Tompkins chemical kinetic model, Vielle's Law pressure-dependent burning, Gruneisen equation-of-state, and simplified strength model were used for the HMX. The propensity for deconsolidation increased with increasing defect size and decreasing initial pressurization, as measured by the increase in burning surface area. These studies are important because they enable the development of continuum-scale damage models and the design of inherently safer explosives.« less

Tensile characteristics of metal nanoparticle films on flexible polymer substrates for printed electronics applications.

PubMed

Kim, Sanghyeok; Won, Sejeong; Sim, Gi-Dong; Park, Inkyu; Lee, Soon-Bok

2013-03-01

Metal nanoparticle solutions are widely used for the fabrication of printed electronic devices. The mechanical properties of the solution-processed metal nanoparticle thin films are very important for the robust and reliable operation of printed electronic devices. In this paper, we report the tensile characteristics of silver nanoparticle (Ag NP) thin films on flexible polymer substrates by observing the microstructures and measuring the electrical resistance under tensile strain. The effects of the annealing temperatures and periods of Ag NP thin films on their failure strains are explained with a microstructural investigation. The maximum failure strain for Ag NP thin film was 6.6% after initial sintering at 150 °C for 30 min. Thermal annealing at higher temperatures for longer periods resulted in a reduction of the maximum failure strain, presumably due to higher porosity and larger pore size. We also found that solution-processed Ag NP thin films have lower failure strains than those of electron beam evaporated Ag thin films due to their highly porous film morphologies.

Material and morphology parameter sensitivity analysis in particulate composite materials

NASA Astrophysics Data System (ADS)

Zhang, Xiaoyu; Oskay, Caglar

2017-12-01

This manuscript presents a novel parameter sensitivity analysis framework for damage and failure modeling of particulate composite materials subjected to dynamic loading. The proposed framework employs global sensitivity analysis to study the variance in the failure response as a function of model parameters. In view of the computational complexity of performing thousands of detailed microstructural simulations to characterize sensitivities, Gaussian process (GP) surrogate modeling is incorporated into the framework. In order to capture the discontinuity in response surfaces, the GP models are integrated with a support vector machine classification algorithm that identifies the discontinuities within response surfaces. The proposed framework is employed to quantify variability and sensitivities in the failure response of polymer bonded particulate energetic materials under dynamic loads to material properties and morphological parameters that define the material microstructure. Particular emphasis is placed on the identification of sensitivity to interfaces between the polymer binder and the energetic particles. The proposed framework has been demonstrated to identify the most consequential material and morphological parameters under vibrational and impact loads.

Phase sensitive thermography for quality assessment of giant magnetostrictive composite materials

NASA Astrophysics Data System (ADS)

Yang, Peng; Law, Chiu T.; Elhajjar, Rani

2017-04-01

Giant magnetostrictive materials are increasingly proposed for smart material applications such as in sensors, actuators, and energy harvesting applications. In a composites form, the materials are combined in particle form with polymer matrix composites. Reviewing the literature on this topic, the reader observes a large amount of variability in the reported properties that are typically based on recording (overall or localized) strain and magnetic field with non-collocating strain gages and a gauss meter, i.e. far field measurements. Previously the linking of the microstructure in magnetostrictive composite to the spatial variability of the localized magnetostrictive response, a significant factor for the composite performance in sensing and acutuation, has not been received adequate attention. In this paper, a full-field phase-sensitive thermography method is proposed to use full-field infrared measurements to infer changes in the microstructure in magnetostrictive polymer composites under a cyclic magnetic field. The results show how defects in the material can be rapidly identified from the proposed approach in inspecting the manufactured smart composites.

Abnormal strong burn-in degradation of highly efficient polymer solar cells caused by spinodal donor-acceptor demixing

PubMed Central

Li, Ning; Perea, José Darío; Kassar, Thaer; Richter, Moses; Heumueller, Thomas; Matt, Gebhard J.; Hou, Yi; Güldal, Nusret S.; Chen, Haiwei; Chen, Shi; Langner, Stefan; Berlinghof, Marvin; Unruh, Tobias; Brabec, Christoph J.

2017-01-01

The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells. PMID:28224984

Computer simulation of heterogeneous polymer photovoltaic devices

NASA Astrophysics Data System (ADS)

Kodali, Hari K.; Ganapathysubramanian, Baskar

2012-04-01

Polymer-based photovoltaic devices have the potential for widespread usage due to their low cost per watt and mechanical flexibility. Efficiencies close to 9.0% have been achieved recently in conjugated polymer based organic solar cells (OSCs). These devices were fabricated using solvent-based processing of electron-donating and electron-accepting materials into the so-called bulk heterojunction (BHJ) architecture. Experimental evidence suggests that a key property determining the power-conversion efficiency of such devices is the final morphological distribution of the donor and acceptor constituents. In order to understand the role of morphology on device performance, we develop a scalable computational framework that efficiently interrogates OSCs to investigate relationships between the morphology at the nano-scale with the device performance. In this work, we extend the Buxton and Clarke model (2007 Modelling Simul. Mater. Sci. Eng. 15 13-26) to simulate realistic devices with complex active layer morphologies using a dimensionally independent, scalable, finite-element method. We incorporate all stages involved in current generation, namely (1) exciton generation and diffusion, (2) charge generation and (3) charge transport in a modular fashion. The numerical challenges encountered during interrogation of realistic microstructures are detailed. We compare each stage of the photovoltaic process for two microstructures: a BHJ morphology and an idealized sawtooth morphology. The results are presented for both two- and three-dimensional structures.

Picosecond laser ablation of poly-L-lactide: Effect of crystallinity on the material response

NASA Astrophysics Data System (ADS)

Ortiz, Rocío; Quintana, Iban; Etxarri, Jon; Lejardi, Ainhoa; Sarasua, Jose-Ramon

2011-11-01

The picosecond laser ablation of poly-L-lactide (PLLA) as a function of laser fluence and degree of crystallinity was examined. The ablation parameters and the surface modifications were analyzed under various irradiation conditions using laser wavelengths ranging from the ultraviolet through the visible. When processing the amorphous PLLA, both energy threshold and topography varied considerably depending on laser wavelength. Laser irradiation showed a reduction in the energy ablation threshold as the degree of crystallinity increased, probably related to photomechanical effects involved in laser ablation with ultra-short pulses and the lower stress accommodation behavior of semicrystalline polymers. In particular, cooperative chain motions are impeded by the higher degree of crystallinity, showing fragile mechanical behavior and lower energy dissipation. The experimental results on ablation rate versus laser energy showed that UV laser ablation on semicrystalline PLLA was more efficient than the visible ablation, i.e., it exhibits higher etch rates over a wide range of pulse energy conditions. These results were interpreted in terms of photo-thermal and photo-chemical response of polymers as a function of material micro-structure and incident laser wavelength. High quality micro-grooves were produced in amorphous PLLA, reveling the potential of ultra-fast laser processing technique in the field of micro-structuring biocompatible and biodegradable polymers for biomedical applications.

A Study on the Deposition of Al2O3 Coatings on Polymer Substrates by a Plasma Spray/Micro-Arc Oxidation Two-Step Method

NASA Astrophysics Data System (ADS)

Sun, Guanhong; He, Xiaodong; Jiang, Jiuxing; Sun, Yue; Zhong, Yesheng

2013-02-01

To increase the wear resistance of polymer matrix composites, alumina coatings were deposited on polymer substrates by a two-step method combining plasma spraying and micro-arc oxidation. The microstructures and phase compositions of the processed coatings were investigated for different treatment times. Uniformly distributed pores were found in addition to the presence of various coral-like structures and floccules on the surface of the coatings. The presence of α-Al2O3 and γ-Al2O3 phases was identified by XRD. The distribution of alumina was analyzed by EDS and is discussed. The maximum bond strength of the coatings was found to be 5.89 MPa. There was little thermal damage in the polymer substrates after the coatings were produced.

How the flow affects the phase behaviour and microstructure of polymer nanocomposites.

PubMed

Stephanou, Pavlos S

2015-02-14

We address the issue of flow effects on the phase behaviour of polymer nanocomposite melts by making use of a recently reported Hamiltonian set of evolution equations developed on principles of non-equilibrium thermodynamics. To this end, we calculate the spinodal curve, by computing values for the nanoparticle radius as a function of the polymer radius-of-gyration for which the second derivative of the generalized free energy of the system becomes zero. Under equilibrium conditions, we recover the phase diagram predicted by Mackay et al. [Science 311, 1740 (2006)]. Under non-equilibrium conditions, we account for the extra terms in the free energy due to changes in the conformations of polymer chains by the shear flow. Overall, our model predicts that flow enhances miscibility, since the corresponding miscibility window opens up for non-zero shear rate values.

Interpenetrating phase ceramic/polymer composite coatings: Fabrication and characterization

NASA Astrophysics Data System (ADS)

Craig, Bradley Dene

The goals of this thesis research were to fabricate interpenetrating phase composite (IPC) ceramic/polymer coatings and to investigate the effect of the interconnected microstructure on the physical and wear properties of the coatings. IPC coatings with an interpenetrating phase microstructure were successfully fabricated by first forming a porous ceramic with an interconnected microstructure using a chemical bonding route (mainly reacting alpha-alumina (0.3 mum) with orthophosphoric acid to form a phosphate bond). Porosity within these ceramic coatings was easily controlled between 20 and 50 vol. % by phosphoric acid addition, and was measured by a new porosity measurement technique (thermogravimetric volatilization of liquids, or TVL) which was developed. The resulting ceramic preforms were infiltrated with a UV and thermally curable cycloaliphatic epoxide resin and cured. This fabrication route resulted in composite coatings with thicknesses ranging from ˜1mum to 100 mum with complete filling of open pore space. The physical properties of the composite coatings, including microhardness, flexural modulus and wear resistance, were evaluated as a function of processing variables, including orthophosphoric acid content and ceramic phase firing temperature, which affected the microstructure and interparticulate bonding between particles in the coatings. For example, microhardness increased from ˜30 on the Vicker's scale to well over 200 as interparticulate bonding was increased in the ceramic phase. Additionally, Taber wear resistance in the best TPC coatings was found to approach that of fully-densified alumina under certain conditions. Several factors were found to influence the wear mechanism in the IPC coating materials. Forming strong connections between ceramic particles led to up to an order of magnitude increase in the wear resistance. Additionally, coating microhardness and ceramic/polymer interfacial strength were studied and found to be important in determining the wear mechanism and wear resistance of IPC composite coatings. A qualitative theory for wear mechanisms in these coatings was developed. Finally, a series of transparent coatings were developed via a similar processing route, using smaller (˜90 nm) boehmite particles instead of 0.3 mum alpha-alumina. Physical property control was found to mimic that found in opaque coatings, and showed increasing surface adsorption characteristics with increasing phosphoric acid content.

Effective response of classical, auxetic and chiral magnetoelastic materials by use of a new variational principle

NASA Astrophysics Data System (ADS)

Danas, K.

2017-08-01

This work provides a rigorous analysis of the effective response, i.e., average magnetization and magnetostriction, of magnetoelastic composites that are subjected to overall magnetic and mechanical loads. It clarifies the differences between a coupled magnetomechanical analysis in which one applies a Eulerian (current) magnetic field and an electroactive one where the Lagrangian (reference) electric field is usually applied. For this, we propose an augmented vector potential variational formulation to carry out numerical periodic homogenization studies of magnetoelastic solids at finite strains and magnetic fields. We show that the developed variational principle can be used for bottom-up design of microstructures with desired magnetomechanical coupling by properly canceling out the macro-geometry and specimen shape effects. To achieve that, we properly treat the average Maxwell stresses arising from the medium surrounding the magnetoelastic representative volume element (RVE), while at the same time we impose a uniform average Eulerian and not Lagrangian magnetic field. The developed variational principle is then used to study a large number of ideal as well as more realistic two-dimensional microstructures. We study the effect of particle volume fraction, particle distribution and particle shape and orientation upon the effective magnetoelastic response at finite strains. We consider also unstructured isotropic microstructures based on random adsorption algorithms and we carry out a convergence study of the representativity of the proposed unit cells. Finally, three-phase two-dimensional auxetic microstructures are analyzed. The first consists of a periodic distribution of voids and particle chains in a polymer matrix, while the second takes advantage of particle shape and chirality to produce negative and positive swelling by proper change of the chirality and the applied magnetic field.

Femtosecond laser microfabrication in polymers towards memory devices and microfluidic applications

NASA Astrophysics Data System (ADS)

Deepak, K. L. N.; Venugopal Rao, S.; Narayana Rao, D.

2011-12-01

We have investigated femtosecond laser induced microstructures, gratings, and craters in four different polymers: poly methyl methacrylate (PMMA), poly dimethyl siloxane (PDMS), polystyrene (PS) and poly vinyl alcohol (PVA) using Ti:sapphire laser delivering 800 nm, 100 femtosecond (fs) pulses at 1 kHz repetition rate with a maximum pulse energy of 1 mJ. Local chemical modifications leading to the formation of optical centers and peroxide radicals which were studied using UV-Visible absorption and emission, confocal micro-Raman and Electron Spin Resonance (ESR) spectroscopic techniques.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan–hyaluronic acid, chitosan–alginic acid, and chitosan–carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Rapid self-assembly of block copolymers to photonic crystals

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

2016-07-05

The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

Visualizing phase transition behavior of dilute stimuli responsive polymer solutions via Mueller matrix polarimetry.

PubMed

Narayanan, Amal; Chandel, Shubham; Ghosh, Nirmalya; De, Priyadarsi

2015-09-15

Probing volume phase transition behavior of superdiluted polymer solutions both micro- and macroscopically still persists as an outstanding challenge. In this regard, we have explored 4 × 4 spectral Mueller matrix measurement and its inverse analysis for excavating the microarchitectural facts about stimuli responsiveness of "smart" polymers. Phase separation behavior of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and pH responsive poly(N,N-(dimethylamino)ethyl methacrylate) (PDMAEMA) and their copolymers were analyzed in terms of Mueller matrix derived polarization parameters, namely, depolarization (Δ), diattenuation (d), and linear retardance (δ). The Δ, d, and δ parameters provided useful information on both macro- and microstructural alterations during the phase separation. Additionally, the two step action ((i) breakage of polymer-water hydrogen bonding and (ii) polymer-polymer aggregation) at the molecular microenvironment during the cloud point generation was successfully probed via these parameters. It is demonstrated that, in comparison to the present techniques available for assessing the hydrophobic-hydrophilic switch over of simple stimuli-responsive polymers, Mueller matrix polarimetry offers an important advantage requiring a few hundred times dilute polymer solution (0.01 mg/mL, 1.1-1.4 μM) at a low-volume format.

Magnetic Resonance Studies of Epoxy Resins.

DTIC Science & Technology

1980-12-07

1. INTRODUCTION ..................................................... ..... ol 2. EPR EXPERIMENTS ON EPOXY RESINS...Calculated sizes of cube-shaped rigid regions.......................... 59 1. INTRODUCTION Epoxy resin polymers are important matrix materials for... information on this network microstructure. The experiments involved measurements made as a function of either temperature or solvent content. In the latter

Efficient 3D porous microstructure reconstruction via Gaussian random field and hybrid optimization.

PubMed

Jiang, Z; Chen, W; Burkhart, C

2013-11-01

Obtaining an accurate three-dimensional (3D) structure of a porous microstructure is important for assessing the material properties based on finite element analysis. Whereas directly obtaining 3D images of the microstructure is impractical under many circumstances, two sets of methods have been developed in literature to generate (reconstruct) 3D microstructure from its 2D images: one characterizes the microstructure based on certain statistical descriptors, typically two-point correlation function and cluster correlation function, and then performs an optimization process to build a 3D structure that matches those statistical descriptors; the other method models the microstructure using stochastic models like a Gaussian random field and generates a 3D structure directly from the function. The former obtains a relatively accurate 3D microstructure, but computationally the optimization process can be very intensive, especially for problems with large image size; the latter generates a 3D microstructure quickly but sacrifices the accuracy due to issues in numerical implementations. A hybrid optimization approach of modelling the 3D porous microstructure of random isotropic two-phase materials is proposed in this paper, which combines the two sets of methods and hence maintains the accuracy of the correlation-based method with improved efficiency. The proposed technique is verified for 3D reconstructions based on silica polymer composite images with different volume fractions. A comparison of the reconstructed microstructures and the optimization histories for both the original correlation-based method and our hybrid approach demonstrates the improved efficiency of the approach. © 2013 The Authors Journal of Microscopy © 2013 Royal Microscopical Society.

Free volume dependent fluorescence property of PMMA composite: Positron annihilation studies

NASA Astrophysics Data System (ADS)

Ravindrachary, V.; Praveena, S. D.; Bhajantri, R. F.; Ismayil, Crasta, Vincent

2013-02-01

The free volume related fluorescence properties of chalcone chromophore [1-(4-methylphenyl)-3-(4-N, N, dimethylaminophenyl)-2-propen-1-one doped Poly(methyl methacrylate) have been studied using fluorescence spectroscopy and Positron Annihilation lifetime spectroscopy techniques. The fluorescence spectra show that the fluorescence behavior depends on the free volume dependent polymer microstructure and varies with dopant concentration with in the composite. The origin and variation of fluorescence is understood by twisted internal charge transfer state as well as free volume. The Positron annihilation study shows that the free volume related microstructure of the composite is vary with doping level.

Fabrication of 3D Carbon Microelectromechanical Systems (C-MEMS).

PubMed

Pramanick, Bidhan; Martinez-Chapa, Sergio O; Madou, Marc; Hwang, Hyundoo

2017-06-17

A wide range of carbon sources are available in nature, with a variety of micro-/nanostructure configurations. Here, a novel technique to fabricate long and hollow glassy carbon microfibers derived from human hairs is introduced. The long and hollow carbon structures were made by the pyrolysis of human hair at 900 °C in a N2 atmosphere. The morphology and chemical composition of natural and pyrolyzed human hairs were investigated using scanning electron microscopy (SEM) and electron-dispersive X-ray spectroscopy (EDX), respectively, to estimate the physical and chemical changes due to pyrolysis. Raman spectroscopy was used to confirm the glassy nature of the carbon microstructures. Pyrolyzed hair carbon was introduced to modify screen-printed carbon electrodes ; the modified electrodes were then applied to the electrochemical sensing of dopamine and ascorbic acid. Sensing performance of the modified sensors was improved as compared to the unmodified sensors. To obtain the desired carbon structure design, carbon micro-/nanoelectromechanical system (C-MEMS/C-NEMS) technology was developed. The most common C-MEMS/C-NEMS fabrication process consists of two steps: (i) the patterning of a carbon-rich base material, such as a photosensitive polymer, using photolithography; and (ii) carbonization through the pyrolysis of the patterned polymer in an oxygen-free environment. The C-MEMS/NEMS process has been widely used to develop microelectronic devices for various applications, including in micro-batteries, supercapacitors, glucose sensors, gas sensors, fuel cells, and triboelectric nanogenerators. Here, recent developments of a high-aspect ratio solid and hollow carbon microstructures with SU8 photoresists are discussed. The structural shrinkage during pyrolysis was investigated using confocal microscopy and SEM. Raman spectroscopy was used to confirm the crystallinity of the structure, and the atomic percentage of the elements present in the material before and after pyrolysis was measured using EDX.

Highly Sensitive Flexible Pressure Sensors Based on Printed Organic Transistors with Centro-Apically Self-Organized Organic Semiconductor Microstructures.

PubMed

Yeo, So Young; Park, Sangsik; Yi, Yeon Jin; Kim, Do Hwan; Lim, Jung Ah

2017-12-13

A highly sensitive pressure sensor based on printed organic transistors with three-dimensionally self-organized organic semiconductor microstructures (3D OSCs) was demonstrated. A unique organic transistor with semiconductor channels positioned at the highest summit of printed cylindrical microstructures was achieved simply by printing an organic semiconductor and polymer blend on the plastic substrate without the use of additional etching or replication processes. A combination of the printed organic semiconductor microstructure and an elastomeric top-gate dielectric resulted in a highly sensitive organic field-effect transistor (FET) pressure sensor with a high pressure sensitivity of 1.07 kPa -1 and a rapid response time of <20 ms with a high reliability over 1000 cycles. The flexibility and high performance of the 3D OSC FET pressure sensor were exploited in the successful application of our sensors to real-time monitoring of the radial artery pulse, which is useful for healthcare monitoring, and to touch sensing in the e-skin of a realistic prosthetic hand.

Laser-induced Self-organizing Microstructures on Steel for Joining with Polymers

NASA Astrophysics Data System (ADS)

van der Straeten, Kira; Burkhardt, Irmela; Olowinsky, Alexander; Gillner, Arnold

The combination of different materials such as thermoplastic composites and metals is an important way to improve lightweight construction. As direct connections between these materials fail due to their physical and chemical properties, other joining techniques are required. A new joining approach besides fastening and adhesive joining is a laser-based two-step process. Within the first step the metal surface is modified by laser-microstructuring. In order to enlarge the boundary surface and create undercuts, random self-organizing microstructures are generated on stainless steel substrates. In a second process step both joining partners, metal and composite, are clamped together, the steel surface is heated up with laser radiation and through heat conduction the thermoplastic matrix is melted and flows into the structures. After cooling-down a firm joint between both materials is created. The presented work shows the influence of different laser parameters on the generation of the microstructures. The joint strength is investigated through tensile shear strength tests.

Electrosteric stabilization of heteroflocculating suspensions and its application to the processing of self-compacting engineered cementitious composites

NASA Astrophysics Data System (ADS)

Kong, Hyun-Joon

This dissertation investigates a dispersion/stabilization technique to improve the fluidity of heteroflocculating concentrated suspensions, and applies the technique to develop self-compacting Engineered Cementitious Composites (ECC), defined as a cementitious material which compacts without any external consolidation in the fresh state, while exhibiting strain-hardening performance in the hardened state. To meet the criteria of micromechanical design to achieve the ductile performance and processing design to attain high fluidity, this work has focused on preparing cement suspensions with low viscosity and high cohesiveness at a particle loading determined by the micromechanical design. Therefore, the goal of this work is to quantify how to adjust the strong flocculation between cement particles due to electrostatic and van der Waals attractive forces. For this purpose, a strong polyelectrolyte, melamine formaldehyde sulfonate (MFS), to disperse the oppositely-charged particles present in the cement dispersion, is combined with a non-ionic polymer, hydroxypropylmethylcellulose (HPMC). The combination of these two polymers to prevent re-flocculation leads to "complementary electrosteric dispersion/ stabilization". With these polymers, suspensions with the desired fluidity for processing are obtained. To quantify the roles of the two polymers in imparting stability, a heteroflocculating model suspension was developed, which facilitates the control of the interactions typical of cement suspensions, but without irreversible hydration. This model suspension is composed of alumina and silica particles, which bear surface potentials of opposite sign at intermediate pHs, as well as has a comparable magnitude of the Hamaker constant as compared to cement particles. As a result, the model system displays not only van der Waals attraction but also electrostatic attraction between dissimilar particles. Rheological studies of the model system stabilized by MFS and HPMC show behavior identical to that of the cement suspensions, allowing the model system to be used to interpret the role of the stabilizers in altering the system microstructure and fluidity. Finally, the self-compacting performance of fresh ECC mixes made with the electrosterically stabilized fresh matrix mix and the ductile strain-hardening performance of the hardened ECC were demonstrated.

A Fully Non-metallic Gas Turbine Engine Enabled by Additive Manufacturing

NASA Technical Reports Server (NTRS)

Grady, Joseph E.

2014-01-01

The Non-Metallic Gas Turbine Engine project, funded by NASA Aeronautics Research Institute (NARI), represents the first comprehensive evaluation of emerging materials and manufacturing technologies that will enable fully nonmetallic gas turbine engines. This will be achieved by assessing the feasibility of using additive manufacturing technologies for fabricating polymer matrix composite (PMC) and ceramic matrix composite (CMC) gas turbine engine components. The benefits of the proposed effort include: 50 weight reduction compared to metallic parts, reduced manufacturing costs due to less machining and no tooling requirements, reduced part count due to net shape single component fabrication, and rapid design change and production iterations. Two high payoff metallic components have been identified for replacement with PMCs and will be fabricated using fused deposition modeling (FDM) with high temperature capable polymer filaments. The first component is an acoustic panel treatment with a honeycomb structure with an integrated back sheet and perforated front sheet. The second component is a compressor inlet guide vane. The CMC effort, which is starting at a lower technology readiness level, will use a binder jet process to fabricate silicon carbide test coupons and demonstration articles. The polymer and ceramic additive manufacturing efforts will advance from monolithic materials toward silicon carbide and carbon fiber reinforced composites for improved properties. Microstructural analysis and mechanical testing will be conducted on the PMC and CMC materials. System studies will assess the benefits of fully nonmetallic gas turbine engine in terms of fuel burn, emissions, reduction of part count, and cost. The proposed effort will be focused on a small 7000 lbf gas turbine engine. However, the concepts are equally applicable to large gas turbine engines. The proposed effort includes a multidisciplinary, multiorganization NASA - industry team that includes experts in ceramic materials and CMCs, polymers and PMCs, structural engineering, additive manufacturing, engine design and analysis, and system analysis.

Enhancement of Local Piezoresponse in Polymer Ferroelectrics via Nanoscale Control of Microstructure

DOE PAGES

Choi, Yoon-Young; Sharma, Pankaj; Phatak, Charudatta; ...

2015-02-01

Polymer ferroelectrics are flexible and lightweight electromechanical materials that are widely studied due to their potential application as sensors, actuators, and energy harvesters. However, one of the biggest challenges is their low piezoelectric coefficient. Here, we report a mechanical annealing effect based on local pressure induced by a nanoscale tip that enhances the local piezoresponse. This process can control the nanoscale material properties over a microscale area at room temperature. We attribute this improvement to the formation and growth of beta-phase extended chain crystals via sliding diffusion and crystal alignment along the scan axis under high mechanical stress. We believemore » that this technique can be useful for local enhancement of piezoresponse in ferroelectric polymer thin films.« less

Fabrication of spherical microlens array by combining lapping on silicon wafer and rapid surface molding

NASA Astrophysics Data System (ADS)

Liu, Xiaohua; Zhou, Tianfeng; Zhang, Lin; Zhou, Wenchen; Yu, Jianfeng; Lee, L. James; Yi, Allen Y.

2018-07-01

Silicon is a promising mold material for compression molding because of its properties of hardness and abrasion resistance. Silicon wafers with carbide-bonded graphene coating and micro-patterns were evaluated as molds for the fabrication of microlens arrays. This study presents an efficient but flexible manufacturing method for microlens arrays that combines a lapping method and a rapid molding procedure. Unlike conventional processes for microstructures on silicon wafers, such as diamond machining and photolithography, this research demonstrates a unique approach by employing precision steel balls and diamond slurries to create microlenses with accurate geometry. The feasibility of this method was demonstrated by the fabrication of several microlens arrays with different aperture sizes and pitches on silicon molds. The geometrical accuracy and surface roughness of the microlens arrays were measured using an optical profiler. The measurement results indicated good agreement with the optical profile of the design. The silicon molds were then used to copy the microstructures onto polymer substrates. The uniformity and quality of the samples molded through rapid surface molding were also assessed and statistically quantified. To further evaluate the optical functionality of the molded microlens arrays, the focal lengths of the microlens arrays were measured using a simple optical setup. The measurements showed that the microlens arrays molded in this research were compatible with conventional manufacturing methods. This research demonstrated an alternative low-cost and efficient method for microstructure fabrication on silicon wafers, together with the follow-up optical molding processes.

Piezoelectric Micro- and Nanostructured Fibers Fabricated from Thermoplastic Nanocomposites Using a Fiber Drawing Technique: Comparative Study and Potential Applications.

PubMed

Lu, Xin; Qu, Hang; Skorobogatiy, Maksim

2017-02-28

We report an all-polymer flexible piezoelectric fiber that uses both judiciously chosen geometry and advanced materials in order to enhance fiber piezoelectric response. The microstructured/nanostructured fiber features a soft hollow polycarbonate core surrounded by a spiral multilayer cladding consisting of alternating layers of piezoelectric nanocomposites (polyvinylidene enhanced with BaTiO 3 , PZT, or CNT) and conductive polymer (carbon-filled polyethylene). The conductive polymer layers serve as two electrodes, and they also form two spatially offset electric connectors on the fiber surface designed for the ease of connectorization. Kilometer-long piezoelectric fibers of sub-millimeter diameters are thermally drawn from a macroscopic preform. The fibers exhibit high output voltage of up to 6 V under moderate bending, and they show excellent mechanical and electrical durability in a cyclic bend-release test. The micron/nanosize multilayer structure enhances in-fiber poling efficiency due to the small distance between the conducting electrodes sandwiching the piezoelectric composite layers. Additionally, the spiral structure greatly increases the active area of the piezoelectric composite, thus promoting higher voltage generation and resulting in 10-100 higher power generation efficiency over the existing piezoelectric cables. Finally, we weave the fabricated piezoelectric fibers into technical textiles and demonstrate their potential applications in power generation when used as a sound detector, smart car seat upholstery, or wearable materials.

New protocol for synthesis of new nanomaterials with continuous 3D networks

NASA Astrophysics Data System (ADS)

Wang, Haiwang; Zhu, Ying; Wei, Xinfang; Chen, Huanhuan; Wang, Ruijie; Zhang, Dong; Song, Huaihe; Song, Shengju

2014-05-01

Nanostructured materials are attractive to researchers because of their unique optical, magnetic, thermodynamic, electrical, mechanical, and chemical properties. Controlling the morphology of nanomaterials could provide structural systems for a wide range of technologies. As a result, the development of nanofabrication techniques that are convenient and offer design flexibility is the subject of many studies. In order to progress beyond the conventional morphologies, we have turned to hydrogels, which can serve as organic templates for nanoscale objects with continuous microstructures. Transmission electron microscopy showed that the obtained nanonetwork had a continuous microstructure, which was several microns in length and width, with a cross-sectional diameter of 5-10 nm synthesized from a 35-g hexamethylenetetramine solution and a 1.5 g Zn(NO3)2 solution, and the cross-sectional diameter can be adjusted from 5 to 200 nm by controlling the concentration of the Zn(NO3)2 solution. Our results also showed that the nanostructures based on a superabsorbent polymer template could be controlled easily in terms of size and morphology by changing the concentration of the reaction solution. This protocol could be easily extended to synthesize a variety of nanostructured materials with novel morphologies.

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. II. Influence of side‐chain structure

PubMed Central

Perevedentsev, Aleksandr; Stavrinou, Paul N.; Smith, Paul

2015-01-01

ABSTRACT Solution‐crystallization is studied for two polyfluorene polymers possessing different side‐chain structures. Thermal analysis and temperature‐dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X‐ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar‐zigzag chain conformation termed the β‐phase, which is observed for certain linear‐side‐chain polyfluorenes, is necessary for the formation of so‐called polymer‐solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side‐chains prevents formation of the β‐phase conformation and results in non‐solvated, i.e. melt‐crystallization‐type, polymer crystals. Unlike non‐solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β‐phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter‐chain interactions. The presented results clarify the fundamental differences between the β‐phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1492–1506 PMID:27546983

Correlating Free-Volume Hole Distribution to the Glass Transition Temperature of Epoxy Polymers.

PubMed

Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

2017-09-07

A new algorithm is developed to quantify the free-volume hole distribution and its evolution in coarse-grained molecular dynamics simulations of polymeric networks. This is achieved by analyzing the geometry of the network rather than a voxelized image of the structure to accurately and efficiently find and quantify free-volume hole distributions within large scale simulations of polymer networks. The free-volume holes are quantified by fitting the largest ellipsoids and spheres in the free-volumes between polymer chains. The free-volume hole distributions calculated from this algorithm are shown to be in excellent agreement with those measured from positron annihilation lifetime spectroscopy (PALS) experiments at different temperature and pressures. Based on the results predicted using this algorithm, an evolution model is proposed for the thermal behavior of an individual free-volume hole. This model is calibrated such that the average radius of free-volumes holes mimics the one predicted from the simulations. The model is then employed to predict the glass-transition temperature of epoxy polymers with different degrees of cross-linking and lengths of prepolymers. Comparison between the predicted glass-transition temperatures and those measured from simulations or experiments implies that this model is capable of successfully predicting the glass-transition temperature of the material using only a PDF of the initial free-volume holes radii of each microstructure. This provides an effective approach for the optimized design of polymeric systems on the basis of the glass-transition temperature, degree of cross-linking, and average length of prepolymers.

Mechanical properties of micro-injected HDPE composites

NASA Astrophysics Data System (ADS)

Bongiorno, A.; Pagano, C.; Agnelli, S.; Baldi, F.; Fassi, I.

2016-03-01

Micro-injection moulding is one of the key manufacturing technologies for the mass production of high value polymeric miniaturized-components. However, this process is not just a straightforward down scaling of the conventional injection moulding technique. Indeed, during the micro-injection the polymer melt is forced to flow at high strain rates through very small channels in non-isothermal conditions, and this can lead to complex microstructures and to parts with unexpected performances. In this work, the relationships among the processing conditions, the mechanical properties and the microstructural characteristics of miniaturized specimens obtained by injection moulding were investigated. Two model systems were considered with the same filler content of 15% wt. (HDPE-talc and HDPE-glass beads), representative of two different types of micro-composites: containing lamellar and spherical micro-particles, respectively. The attention was focused on the influence of the filler type and the process conditions on the mechanical behaviour, examined by uniaxial tensile tests and dynamic-mechanical analyses, and on the morphological characteristics of the specimens, examined by microscopy analyses. The results highlight that mechanical response of the miniaturized specimens is significantly affected by both the filler and the process conditions that can have an influence on the polymer microstructure. Lamellar composites showed the best performance due to the orientation of the talc particles during the micro-injection process, while, different morphologies of the skin/core transition region in dependence on the process temperatures were observable.

The microstructure of capsule containing self-healing materials: A micro-computed tomography study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Stappen, Jeroen, E-mail: Jeroen.Vanstappen@uge

Autonomic self-healing materials are materials with built-in (micro-) capsules or vessels, which upon fracturing release healing agents in order to recover the material's physical and mechanical properties. In order to better understand and engineer these materials, a thorough characterization of the material's microstructural behavior is essential and often overlooked. In this context, micro-computed tomography (μCT) can be used to investigate the three dimensional distribution and (de)bonding of (micro-) capsules in their native state in a polymer system with self-healing properties. Furthermore, in-situ μCT experiments in a self-healing polymer and a self-healing concrete system can elucidate the breakage and leakage behaviormore » of (micro-) capsules at the micrometer scale. While challenges related to image resolution and contrast complicate the characterization in specific cases, non-destructive 3D imaging with μCT is shown to contribute to the understanding of the link between the microstructure and the self-healing behavior of these complex materials. - Highlights: • μCT imaging allows for the analysis of microcapsule distribution patterns in self-healing materials. • μCT allows for qualitative and quantitative measurements of healing agent release from carriers in self-healing materials. • Experimental set-ups can be optimized by changing chemical compounds in the system to ensure maximum quality imaging.« less

Molecular modeling of polymer composite interactions with analytes in electronic nose sensors for environmental monitoring in International Space Station

NASA Technical Reports Server (NTRS)

Shevade, A. V.; Ryan, M. A.; Homer, M. L.; Manfreda, A. M.; Zhou, H.; Manatt, K.

2002-01-01

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL Electronic Nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings (with no hydrogens). The Dreiding 2.21 force field is used for the polymer and solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4- vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic (ammonia) and organic (methanol, toluene, hydrazine) compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites.

Molecular modeling of polymer composite-analyte interactions in electronic nose sensors

NASA Technical Reports Server (NTRS)

Shevade, A. V.; Ryan, M. A.; Homer, M. L.; Manfreda, A. M.; Zhou, H.; Manatt, K. S.

2003-01-01

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL electronic nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereoisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings with no hydrogens. The Dreiding 2.21 force field is used for the polymer, solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4-vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic and organic compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites. c2003 Elsevier Science B.V. All rights reserved.

Enhanced gas separation factors of microporous polymer constrained in the channels of anodic alumina membranes

PubMed Central

Chernova, Ekaterina; Petukhov, Dmitrii; Boytsova, Olga; Alentiev, Alexander; Budd, Peter; Yampolskii, Yuri; Eliseev, Andrei

2016-01-01

New composite membranes based on porous anodic alumina films and polymer of intrinsic microporosity (PIM-1) have been prepared using a spin-coating technique. According to scanning electron microscopy, partial penetration of polymer into the pores of alumina supports takes place giving rise to selective polymeric layers with fiber-like microstructure. Geometric confinement of rigid PIM-1 in the channels of anodic alumina causes reduction of small-scale mobility in polymeric chains. As a result, transport of permanent gases, such as CH4, becomes significantly hindered across composite membranes. Contrary, the transport of condensable gases (CO2, С4H10), did not significantly suffer from the confinement due to high solubility in the polymer matrix. This strategy enables enhancement of selectivity towards CO2 and C4H10 without significant loss of the membrane performance and seems to be prospective for drain and sweetening of natural gas. PMID:27498607

Enhanced gas separation factors of microporous polymer constrained in the channels of anodic alumina membranes

NASA Astrophysics Data System (ADS)

Chernova, Ekaterina; Petukhov, Dmitrii; Boytsova, Olga; Alentiev, Alexander; Budd, Peter; Yampolskii, Yuri; Eliseev, Andrei

2016-08-01

New composite membranes based on porous anodic alumina films and polymer of intrinsic microporosity (PIM-1) have been prepared using a spin-coating technique. According to scanning electron microscopy, partial penetration of polymer into the pores of alumina supports takes place giving rise to selective polymeric layers with fiber-like microstructure. Geometric confinement of rigid PIM-1 in the channels of anodic alumina causes reduction of small-scale mobility in polymeric chains. As a result, transport of permanent gases, such as CH4, becomes significantly hindered across composite membranes. Contrary, the transport of condensable gases (CO2, С4H10), did not significantly suffer from the confinement due to high solubility in the polymer matrix. This strategy enables enhancement of selectivity towards CO2 and C4H10 without significant loss of the membrane performance and seems to be prospective for drain and sweetening of natural gas.

Preparation, anti-biofouling and drag-reduction properties of a biomimetic shark skin surface

PubMed Central

Pu, Xia; Li, Guangji; Huang, Hanlu

2016-01-01

ABSTRACT Shark skin surfaces show non-smoothness characteristics due to the presence of a riblet structure. In this study, biomimetic shark skin was prepared by using the polydimethylsiloxane (PDMS)-embedded elastomeric stamping (PEES) method. Scanning electron microscopy (SEM) was used to examine the surface microstructure and fine structure of shark skin and biomimetic shark skin. To analyse the hydrophobic mechanism of the shark skin surface microstructure, the effect of biomimetic shark skin surface microstructure on surface wettability was evaluated by recording water contact angle. Additionally, protein adhesion experiments and anti-algae adhesion performance testing experiments were used to investigate and evaluate the anti-biofouling properties of the surface microstructure of biomimetic shark skin. The recorded values of the water contact angle of differently microstructured surfaces revealed that specific microstructures have certain effects on surface wettability. The anti-biofouling properties of the biomimetic shark skin surface with microstructures were superior to a smooth surface using the same polymers as substrates. Moreover, the air layer fixed on the surface of the biomimetic shark skin was found to play a key role in their antibiont adhesion property. An experiment into drag reduction was also conducted. Based on the experimental results, the microstructured surface of the prepared biomimetic shark skin played a significant role in reducing drag. The maximum of drag reduction rate is 12.5%, which is higher than the corresponding maximum drag reduction rate of membrane material with a smooth surface. PMID:26941105

Preparation, anti-biofouling and drag-reduction properties of a biomimetic shark skin surface.

PubMed

Pu, Xia; Li, Guangji; Huang, Hanlu

2016-04-15

Shark skin surfaces show non-smoothness characteristics due to the presence of a riblet structure. In this study, biomimetic shark skin was prepared by using the polydimethylsiloxane (PDMS)-embedded elastomeric stamping (PEES) method. Scanning electron microscopy (SEM) was used to examine the surface microstructure and fine structure of shark skin and biomimetic shark skin. To analyse the hydrophobic mechanism of the shark skin surface microstructure, the effect of biomimetic shark skin surface microstructure on surface wettability was evaluated by recording water contact angle. Additionally, protein adhesion experiments and anti-algae adhesion performance testing experiments were used to investigate and evaluate the anti-biofouling properties of the surface microstructure of biomimetic shark skin. The recorded values of the water contact angle of differently microstructured surfaces revealed that specific microstructures have certain effects on surface wettability. The anti-biofouling properties of the biomimetic shark skin surface with microstructures were superior to a smooth surface using the same polymers as substrates. Moreover, the air layer fixed on the surface of the biomimetic shark skin was found to play a key role in their antibiont adhesion property. An experiment into drag reduction was also conducted. Based on the experimental results, the microstructured surface of the prepared biomimetic shark skin played a significant role in reducing drag. The maximum of drag reduction rate is 12.5%, which is higher than the corresponding maximum drag reduction rate of membrane material with a smooth surface. © 2016. Published by The Company of Biologists Ltd.

Metal Composition and Polyethylenimine Doping Capacity Effects on Semiconducting Metal Oxide-Polymer Blend Charge Transport.

PubMed

Huang, Wei; Guo, Peijun; Zeng, Li; Li, Ran; Wang, Binghao; Wang, Gang; Zhang, Xinan; Chang, Robert P H; Yu, Junsheng; Bedzyk, Michael J; Marks, Tobin J; Facchetti, Antonio

2018-04-25

Charge transport and film microstructure evolution are investigated in a series of polyethylenimine (PEI)-doped (0.0-6.0 wt%) amorphous metal oxide (MO) semiconductor thin film blends. Here, PEI doping generality is broadened from binary In 2 O 3 to ternary (e.g., In+Zn in IZO, In+Ga in IGO) and quaternary (e.g., In+Zn+Ga in IGZO) systems, demonstrating the universality of this approach for polymer electron doping of MO matrices. Systematic comparison of the effects of various metal ions on the electronic transport and film microstructure of these blends are investigated by combined thin-film transistor (TFT) response, AFM, XPS, XRD, X-ray reflectivity, and cross-sectional TEM. Morphological analysis reveals that layered MO film microstructures predominate in PEI-In 2 O 3 , but become less distinct in IGO and are not detectable in IZO and IGZO. TFT charge transport measurements indicate a general coincidence of a peak in carrier mobility (μ peak ) and overall TFT performance at optimal PEI doping concentrations. Optimal PEI loadings that yield μ peak values depend not only on the MO elemental composition but also, equally important, on the metal atomic ratios. By investigating the relationship between the MO energy levels and PEI doping by UPS, it is concluded that the efficiency of PEI electron-donation is highly dependent on the metal oxide matrix work function in cases where film morphology is optimal, as in the IGO compositions. The results of this investigation demonstrate the broad generality and efficacy of PEI electron doping applied to electronically functional metal oxide systems and that the resulting film microstructure, morphology, and energy level modifications are all vital to understanding charge transport in these amorphous oxide blends.

PVA/NaCl/MgO nanocomposites-microstructural analysis by whole pattern fitting method

NASA Astrophysics Data System (ADS)

Prashanth, K. S.; Mahesh, S. S.; Prakash, M. B. Nanda; Somashekar, R.; Nagabhushana, B. M.

2018-04-01

The nanofillers in the macromolecular matrix have displayed noteworthy changes in the structure and reactivity of the polymer nanocomposites. Novel functional materials usually consist of defects and are largely disordered. The intriguing properties of these materials are often attributed to defects. X-ray line profiles from powder diffraction reveal the quantitative information about size distribution and shape of diffracting domains which governs the contribution from small conventional X-ray diffraction (XRD) techniques to enumerate the microstructural information. In this study the MgO nanoparticles were prepared by solution combustion method and PVA/NaCl/MgO nanocomposite films were synthesized by the solvent cast method. Microstructural parameters viz crystal defects like stacking faults and twin faults, compositional inhomogeneity, crystallite size and lattice strain (g in %), were extracted using whole pattern fitting method.

Inexpensive, rapid fabrication of polymer-film microfluidic autoregulatory valve for disposable microfluidics.

PubMed

Zhang, Xinjie; Zhu, Zhixian; Ni, Zhonghua; Xiang, Nan; Yi, Hong

2017-06-01

This work presents the fabrication of a microfluidic autoregulatory valve which is composed of several layers of thin polymer films (i.e., polyvinyl chloride (PVC), polyethylene terephthalate (PET) double-sided tape, and polydimethylsiloxane (PDMS)). Briefly, pulsed UV laser is employed to cut the microstructures of through grooves or holes in the thermoplastic polymer films, and then the polymer-film valves are precisely assembled through laminating the PDMS membranes to the thermoplastic polymer films through the roll-lamination method. The effective bonding between the PVC film and the PDMS membrane is realized using the planar seal method, and the valve is sandwiched and compressed by a home-made housing to achieve the good seal effect. Then, the flow performances of the prototype valve are examined, and constant flow autoregulation is realized under the static or dynamic test pressures. The long-term response of the valve is also studied and minimum flow-rate decrements are found over a long actuation time. The fabrication method proposed in this work is successful for the low-cost and fast prototyping of the polymer-film valve. We believe our method will also be broadly applicable for fabrication of other low-cost and disposable polymer-film microfluidic devices.

Preliminary Findings from the SHERE ISS Experiment

NASA Technical Reports Server (NTRS)

Hall, Nancy R.; McKinley, Gareth H.; Erni, Philipp; Soulages, Johannes; Magee, Kevin S.

2009-01-01

The Shear History Extensional Rheology Experiment (SHERE) is an International Space Station (ISS) glovebox experiment designed to study the effect of preshear on the transient evolution of the microstructure and viscoelastic tensile stresses for monodisperse dilute polymer solutions. The SHERE experiment hardware was launched on Shuttle Mission STS-120 (ISS Flight 10A) on October 22, 2007, and 20 fluid samples were launched on Shuttle Mission STS-123 (ISS Flight 10/A) on March 11, 2008. Astronaut Gregory Chamitoff performed experiments during Increment 17 on the ISS between June and September 2008. A summary of the ten year history of the hardware development, the experiment's science objectives, and Increment 17's flight operations are discussed in the paper. A brief summary of the preliminary science results is also discussed.

3D Printing of Living Responsive Materials and Devices.

PubMed

Liu, Xinyue; Yuk, Hyunwoo; Lin, Shaoting; Parada, German Alberto; Tang, Tzu-Chieh; Tham, Eléonore; de la Fuente-Nunez, Cesar; Lu, Timothy K; Zhao, Xuanhe

2018-01-01

3D printing has been intensively explored to fabricate customized structures of responsive materials including hydrogels, liquid-crystal elastomers, shape-memory polymers, and aqueous droplets. Herein, a new method and material system capable of 3D-printing hydrogel inks with programed bacterial cells as responsive components into large-scale (3 cm), high-resolution (30 μm) living materials, where the cells can communicate and process signals in a programmable manner, are reported. The design of 3D-printed living materials is guided by quantitative models that account for the responses of programed cells in printed microstructures of hydrogels. Novel living devices are further demonstrated, enabled by 3D printing of programed cells, including logic gates, spatiotemporally responsive patterning, and wearable devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational discovery of extremal microstructure families

PubMed Central

Chen, Desai; Skouras, Mélina; Zhu, Bo; Matusik, Wojciech

2018-01-01

Modern fabrication techniques, such as additive manufacturing, can be used to create materials with complex custom internal structures. These engineered materials exhibit a much broader range of bulk properties than their base materials and are typically referred to as metamaterials or microstructures. Although metamaterials with extraordinary properties have many applications, designing them is very difficult and is generally done by hand. We propose a computational approach to discover families of microstructures with extremal macroscale properties automatically. Using efficient simulation and sampling techniques, we compute the space of mechanical properties covered by physically realizable microstructures. Our system then clusters microstructures with common topologies into families. Parameterized templates are eventually extracted from families to generate new microstructure designs. We demonstrate these capabilities on the computational design of mechanical metamaterials and present five auxetic microstructure families with extremal elastic material properties. Our study opens the way for the completely automated discovery of extremal microstructures across multiple domains of physics, including applications reliant on thermal, electrical, and magnetic properties. PMID:29376124

Straightforward and precise approach to replicate complex hierarchical structures from plant surfaces onto soft matter polymer

PubMed Central

Speck, Thomas; Bohn, Holger F.

2018-01-01

The surfaces of plant leaves are rarely smooth and often possess a species-specific micro- and/or nano-structuring. These structures usually influence the surface functionality of the leaves such as wettability, optical properties, friction and adhesion in insect–plant interactions. This work presents a simple, convenient, inexpensive and precise two-step micro-replication technique to transfer surface microstructures of plant leaves onto highly transparent soft polymer material. Leaves of three different plants with variable size (0.5–100 µm), shape and complexity (hierarchical levels) of their surface microstructures were selected as model bio-templates. A thermoset epoxy resin was used at ambient conditions to produce negative moulds directly from fresh plant leaves. An alkaline chemical treatment was established to remove the entirety of the leaf material from the cured negative epoxy mould when necessary, i.e. for highly complex hierarchical structures. Obtained moulds were filled up afterwards with low viscosity silicone elastomer (PDMS) to obtain positive surface replicas. Comparative scanning electron microscopy investigations (original plant leaves and replicated polymeric surfaces) reveal the high precision and versatility of this replication technique. This technique has promising future application for the development of bioinspired functional surfaces. Additionally, the fabricated polymer replicas provide a model to systematically investigate the structural key points of surface functionalities. PMID:29765666

Method and apparatus for measuring micro structures, anisotropy and birefringence in polymers using laser scattered light

DOEpatents

Grek, Boris; Bartolick, Joseph; Kennedy, Alan D.

2000-01-01

A method and apparatus for measuring microstructures, anistropy and birefringence in polymers using laser scattered light includes a laser which provides a beam that can be conditioned and is directed at a fiber or film which causes the beam to scatter. Backscatter light is received and processed with detectors and beam splitters to obtain data. The data is directed to a computer where it is processed to obtain information about the fiber or film, such as the birefringence and diameter. This information provides a basis for modifications to the production process to enhance the process.

Micromechanics of fatigue in woven and stitched composites

NASA Technical Reports Server (NTRS)

Cox, B. N.; Dadkhah, M. S.; Inman, R. V.; Mitchell, M. R.; Morris, W. L.; Schroeder, S.

1991-01-01

The goal is to determine how microstructural factors, especially the architecture of microstructural factors, control fatigue damage in 3D reinforced polymer composites. Test materials were fabricated from various preforms, including stitched quasi-isotropic laminates, and through-the-thickness angle interlock, layer-to-layer angle interlock, and through-the-thickness stitching effect weaves. Preforms were impregnated with a tough resin by a special vacuum infiltration method. Most tests are being performed in uniaxial compression/compression loading. In all cases to date, failure has occurred not by delamination, but by shear failure, which occurs suddenly rather than by gradual macroscopic crack growth. Some theoretical aspects of bridging are also examined.

Nanocomposite capsules with directional, pulsed nanoparticle release.

PubMed

Udoh, Christiana E; Cabral, João T; Garbin, Valeria

2017-12-01

The precise spatiotemporal delivery of nanoparticles from polymeric capsules is required for applications ranging from medicine to materials science. These capsules derive key performance aspects from their overall shape and dimensions, porosity, and internal microstructure. To this effect, microfluidics provide an exceptional platform for emulsification and subsequent capsule formation. However, facile and robust approaches for nanocomposite capsule fabrication, exhibiting triggered nanoparticle release, remain elusive because of the complex coupling of polymer-nanoparticle phase behavior, diffusion, phase inversion, and directional solidification. We investigate a model system of polyelectrolyte sodium poly(styrene sulfonate) and 22-nm colloidal silica and demonstrate a robust capsule morphology diagram, achieving a range of internal morphologies, including nucleated and bicontinuous microstructures, as well as isotropic and non-isotropic external shapes. Upon dissolution in water, we find that capsules formed with either neat polymers or neat nanoparticles dissolve rapidly and isotropically, whereas bicontinuous, hierarchical, composite capsules dissolve via directional pulses of nanoparticle clusters without disrupting the scaffold, with time scales tunable from seconds to hours. The versatility, facile assembly, and response of these nanocomposite capsules thus show great promise in precision delivery.

Dually actuated triple shape memory polymers of cross-linked polycyclooctene-carbon nanotube/polyethylene nanocomposites.

PubMed

Wang, Zhenwen; Zhao, Jun; Chen, Min; Yang, Minhao; Tang, Luyang; Dang, Zhi-Min; Chen, Fenghua; Huang, Miaoming; Dong, Xia

2014-11-26

In this work, electrically and thermally actuated triple shape memory polymers (SMPs) of chemically cross-linked polycyclooctene (PCO)-multiwalled carbon nanotube (MWCNT)/polyethylene (PE) nanocomposites with co-continuous structure and selective distribution of fillers in PCO phase are prepared. We systematically studied not only the microstructure including morphology and fillers' selective distribution in one phase of the PCO/PE blends, but also the macroscopic properties including thermal, mechanical, and electrical properties. The co-continuous window of the immiscible PCO/PE blends is found to be the volume fraction of PCO (vPCO) of ca. 40-70 vol %. The selective distribution of fillers in one phase of co-continuous blends is obtained by a masterbatch technique. The prepared triple SMP materials show pronounced triple shape memory effects (SMEs) on the dynamic mechanical thermal analysis (DMTA) and the visual observation by both thermal and electric actuations. Such polyolefin samples with well-defined microstructure, electrical actuation, and triple SMEs might have potential applications as, for example, multiple autochoke elements for engines, self-adjusting orthodontic wires, and ophthalmic devices.

A Printing-Centric Approach to the Electrostatic Modification of Polymer/Clay Composites for use in 3D Direct-Ink Writing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rauzan, Brittany; Lehman, Sean; McCracken, Josell

Polymer/clay composite inks are exceptionally useful materials for fabrication processes based on 3D direct-ink writing, however, there remains an insufficient understanding of how their physiochemical dynamics impact printability. Using a model system, N-isopropylacrylamide/Laponite, the electrostatic interactions between Laponite platelets are modified to tune critical rheological properties in order to improve printability. Rheological measurements and X-ray scattering experiments are carried out to monitor the nano/micro-structural dynamics and complex physicochemical interactions of Laponite as it impacts complex modulus in the linear region, flow behavior, thixotropy, and yield stress of the composite ink. Modification of the electrostatic interactions between platelets reduces the yieldmore » stress of the material, while maintaining a complex microstructure that allows for sufficient recovery times upon removal of stress to form stable, and thus printable, filaments. A printing-centric approach is established based on a fundamental understanding of electrostatic inter-particle interactions, harnessing the innate microstructure of Laponite in 3D direct-ink writing of composites.« less

Processable conductive graphene/polyethylene nanocomposites: Effects of graphene dispersion and polyethylene blending with oxidized polyethylene on rheology and microstructure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iqbal, Muhammad Z.; Abdala, Ahmed A.; Mittal, Vikas

Poor dispersion of graphene in non-polar polymer matrices creates composites with limited applications. A method to improve the dispersion of graphene in polyethylene (PE) via blending PE with oxidized PE (OPE) is examined. Graphene was produced by simultaneous thermal exfoliation and reduction of graphite oxide. Nanocomposites of graphene with PE as well as graphene with PE/OPE-blends were prepared by solvent blending. Improved dispersion of graphene in PE/OPE blends substantially decreases percolation from both rheological (0.3 vol%) and electrical (0.13 vol%) measurements compared to neat PE nanocomposites (1 and 0.29 vol%), respectively. A universal Brownian dispersion of graphene in polymers wasmore » concluded similar to that of nanotubes, following the Doi-Edwards theory. Micromechanical models, such as Mori-Tanaka and Halpin-Tsai models, modeled the mechanical properties of the nanocomposites. The nanocomposites microstructure, studied by small angle x-ray scattering, confirmed better dispersion of graphene at lower loadings and the formation of surface fractals in the blend/graphene nanocomposites; whereas only mass fractals were observed in neat PE/graphene nanocomposites.« less

Characterisation and microstructure of reduced-fat chicken patties made with a novel polymer from Agrobacterium radiobacter k84.

PubMed

Calliari, Caroline Maria; de Souza, Evandro Leite; Castro-Goméz, Raúl Jorge Hernan; Honório, Vanessa Gonçalves; Magnani, Marciane

2015-04-15

Chicken patties elaborated with a novel polymer from Agrobacterium radiobacter k84 (ARB) were characterised during 60days of frozen storage. After cooking, formulations without ARB (F0), with ARB 5 g/100 g (F5) and ARB 10 g/100 g (F10) presented 4.23%, 2.83% and 0.11% fat, respectively. No differences were observed to water holding capacity, cooking yield and shear force among formulations. Microstructural analysis showed formation of meat emulsion for F5 and gel for F10. Colour and chicken flavour decreased with increase of ARB; no difference was found for tenderness among the formulations. Overall acceptance showed higher scores for F0 when compared to F5 and F10. Lipid oxidation was not a limiting factor for stability of patties; all formulations presented suitable microbiological quality over the assessed period. These results suggest ARB as a promising fat substitute, capable of maintain the quality aspects of chicken patties, although a negative impact in colour has been found. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis of Three-dimensional Polymer Nanostructures via Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Cheng, Kenneth

Chemical vapor deposition (CVD) is a widely practiced methodology for preparing thin film polymer coatings, and the coatings can be applied to a broad range of materials, including three-dimensional solid structures and low-vapor pressure liquids. Reactive poly(p-xylylene) (PPX) coatings prepared by CVD can be used as a powerful tool for surface functionalization and bio-conjugation. The first portion of this dissertation serves to extend the use of CVD-based reactive PPX coatings as a surface functionalization strategy for the conjugation of biomolecules. Micro-structured PPX coatings having multiple surface reactive groups were fabricated. Multiple orthogonal click reactions were then employed to selectively immobilize galactose and mannobiose to the micro-structured polymer coatings. The presence of different types of carbohydrate enables lectins binding for examining ligands/cell receptor interactions. This dissertation also demonstrates the use of CVD-based reactive PPX coatings as intermediate layers to immobilize adenoviral vectors onto tissue scaffolds. The ability to tether adenoviral vectors on tissue scaffolds localizes the transduction near the scaffold surface and reduces acute toxicity and hepatic pathology cause by direct administration of the viral vector, providing a safe and efficient gene therapy delivery strategy. In the second portion of this dissertation, we explore the CVD of PPX onto surfaces coated with a thin layer of liquid crystal (LC). Instead of forming a conformal PPX coating encapsulating the LC layer, PPX assembled into an array of high-aspect ratio nanofibers inside the LC layer. The LC layer was demonstrated to act as a template where the anisotropic internal ordering of the LC facilitated the formation of nanofibers. The diameter of the nanofibers was in the range of 100 nm and could be tuned by type of LC template used, and the length of the nanofibers could be precisely controlled by varying the thickness of the LC film. The overall shape of the nanofibers could be controlled by the internal ordering of the LC template, as exemplified by the assembly of helical nanofibers using cholesteric LC as the template. PPX nanofibers could be applied to a broad range of materials, such as curved surface, metal meshes and microparticles. We successfully created nanofibers with different surface functionalities and utilized them to capture molecules of interest. We also demonstrated the synthesis of twisted nanofibers using chiral-substituted precursors. The direction and the degree of twisting of nanofibers could be controlled by the handedness and the enantiomeric excess of the chiral precursor. Finally, we showed that the LC-templated CVD method could be extended to fabricating nanofibers made of other CVD-based polymer systems, such as poly(lutidine) and poly(p-phenylene vinylene). Our work opens a new platform for designing functional polymer nanostructures with programmable geometry, alignment and chemistry. The polymer nanostructures can be attractive for applications ranging from sensors, affinity filtration, and catalytic supports.

Cyclopentadithiophene-Benzothiadiazole Donor-Acceptor Polymers as Prototypical Semiconductors for High-Performance Field-Effect Transistors.

PubMed

Li, Mengmeng; An, Cunbin; Pisula, Wojciech; Müllen, Klaus

2018-05-15

Donor-acceptor (D-A) conjugated polymers are of great interest as organic semiconductors, because they offer a rational tailoring of the electronic properties by modification of the donor and acceptor units. Nowadays, D-A polymers exhibit field-effect mobilities on the order of 10 -2 -10 0 cm 2 V -1 s -1 , while several examples showed a mobility over 10 cm 2 V -1 s -1 . The development of cyclopentadithiophene-benzothiadiazole (CDT-BTZ) copolymers one decade ago represents an important step toward high-performance organic semiconductors for field-effect transistors. The significant rise in field-effect mobility of CDT-BTZ in comparison to the existing D-A polymers at that time opened the door to a new research field with a large number of novel D-A systems. From this point, the device performance of CDT-BTZ was gradually improved by a systematic optimization of the synthesis and polymer structure as well as by an efficient solution processing into long-range ordered thin films. The key aspect was a comprehensive understanding of the relation between polymer structure and solid-state organization. Due to their fundamental role for the field of D-A polymers in general, this Account will for the first time explicitly focus on prototypical CDT-BTZ polymers, while other reviews provide an excellent general overview on D-A polymers. The first part of this Account discusses strategies for improving the charge carrier transport, focusing on chemical aspects. Improved synthesis as an essential stage toward high purity, and high molecular weight is a prerequisite for molecular order. The modification of substituents is a further crucial feature to tune the CDT-BTZ packing and self-assembly. Linear alkyl side chains facilitate intermolecular π-stacking interactions, while branched ones increase solubility and alter the polymer packing. Additional control over the supramolecular organization of CDT-BTZ polymers is introduced by alkenyl substituents via their cis-trans isomerization. The last discussed chemical concept is based on heteroatom variation within the CDT unit. The relationships found experimentally for CDT-BTZ between polymer chemical structure, solid-state organization, and charge carrier transport are explained by means of theoretical simulations. Besides the effects of molecular design, the second part of this Account discusses the processing conditions from solution. The film microstructure, defined as a mesoscopic domain organization, is critically affected by solution processing. Suitable processing techniques allow the formation of a long-range order and a uniaxial orientation of the CDT-BTZ chains, thus lowering the trapping density of grain boundaries for charge carriers. For instance, alignment of the CDT-BTZ polymer by dip-coating yields films with a pronounced structural and electrical anisotropy and favors a fast migration of charge carriers along the conjugated backbones in the deposition direction. By using film compression with the assistance of an ionic liquid, one even obtains CDT-BTZ films with a band-like transport and a transistor hole mobility of 10 cm 2 V -1 s -1 . This device performance is attributed to large domains in the compressed films being formed by CDT-BTZ with longer alkyl chains, which establish a fine balance between polymer interactions and growth kinetics during solvent evaporation. On the basis of the prototypical semiconductor CDT-BTZ, this Account provides general guidelines for achieving high-performance polymer transistors by taking into account the subtle balance of synthetic protocol, molecular design, and processing.

Polymer-based materials to be used as the active element in microsensors: a scanning force microscopy study

PubMed

Porter; Eastman; Pace; Bradley

2000-09-01

Polymer-based materials can be incorporated as the active sensing elements in chemiresistor devices. Most of these devices take advantage of the fact that certain polymers will swell when exposed to gaseous analytes. To measure this response, a conducting material such as carbon black is incorporated within the nonconducting polymer matrix. In response to analytes, polymer swelling results in a measurable change in the conductivity of the polymer/carbon composite material. Arrays of these sensors may be used in conjunction with pattern recognition techniques for purposes of analyte recognition and quantification. We have used the technique of scanning force microscopy (SFM) to investigate microstructural changes in carbon-polymer composites formed from the polymers poly (isobutylene) (PIB), poly (vinyl alcohol) (PVA), and poly (ethylene-vinyl acetate) (PEVA) when exposed to the analytes hexane, toluene, water, ethanol, and acetone. Using phase-contrast imaging (PI), changes in the carbon nanoparticle distribution on the surface of the polymer matrix are measured as the polymers are exposed to the analytes in vapor phase. In some but not all cases, the changes were reversible (at the scale of the SFM measurements) upon removal of the analyte vapor. In this paper, we also describe a new type of microsensor based on piezoresistive microcantilever technology. With these new devices, polymeric volume changes accompanying exposure to analyte vapor are measured directly by a piezoresistive microcantilever in direct contact with the polymer. These devices may offer a number of advantages over standard chemiresistor-based sensors.

High strain rate behaviour of polypropylene microfoams

NASA Astrophysics Data System (ADS)

Gómez-del Río, T.; Garrido, M. A.; Rodríguez, J.; Arencón, D.; Martínez, A. B.

2012-08-01

Microcellular materials such as polypropylene foams are often used in protective applications and passive safety for packaging (electronic components, aeronautical structures, food, etc.) or personal safety (helmets, knee-pads, etc.). In such applications the foams which are used are often designed to absorb the maximum energy and are generally subjected to severe loadings involving high strain rates. The manufacture process to obtain polymeric microcellular foams is based on the polymer saturation with a supercritical gas, at high temperature and pressure. This method presents several advantages over the conventional injection moulding techniques which make it industrially feasible. However, the effect of processing conditions such as blowing agent, concentration and microfoaming time and/or temperature on the microstructure of the resulting microcellular polymer (density, cell size and geometry) is not yet set up. The compressive mechanical behaviour of several microcellular polypropylene foams has been investigated over a wide range of strain rates (0.001 to 3000 s-1) in order to show the effects of the processing parameters and strain rate on the mechanical properties. High strain rate tests were performed using a Split Hopkinson Pressure Bar apparatus (SHPB). Polypropylene and polyethylene-ethylene block copolymer foams of various densities were considered.

Chemical and microstructural characterizations of plasma polymer films by time-of-flight secondary ion mass spectrometry and principal component analysis

NASA Astrophysics Data System (ADS)

Cossement, Damien; Renaux, Fabian; Thiry, Damien; Ligot, Sylvie; Francq, Rémy; Snyders, Rony

2015-11-01

It is accepted that the macroscopic properties of functional plasma polymer films (PPF) are defined by their functional density and their crosslinking degree (χ) which are quantities that most of the time behave in opposite trends. If the PPF chemistry is relatively easy to evaluate, it is much more challenging for χ. This paper reviews the recent work developed in our group on the application of principal component analysis (PCA) to time-of-flight secondary ion mass spectrometric (ToF-SIMS) positive spectra data in order to extract the relative cross-linking degree (χ) of PPF. NH2-, COOR- and SH-containing PPF synthesized in our group by plasma enhanced chemical vapor deposition (PECVD) varying the applied radiofrequency power (PRF), have been used as model surfaces. For the three plasma polymer families, the scores of the first computed principal component (PC1) highlighted significant differences in the chemical composition supported by X-Ray photoelectron spectroscopy (XPS) data. The most important fragments contributing to PC1 (loadings > 90%) were used to compute an average C/H ratio index for samples synthesized at low and high PRF. This ratio being an evaluation of χ, these data, accordingly to the literature, indicates an increase of χ with PRF excepted for the SH-PPF. These results have been cross-checked by the evaluation of functional properties of the plasma polymers namely a linear correlation with the stability of NH2-PPF in ethanol and a correlation with the mechanical properties of the COOR-PPF. For the SH-PPF family, the peculiar evolution of χ is supported by the understanding of the growth mechanism of the PPF from plasma diagnostic. The whole set of data clearly demonstrates the potential of the PCA method for extracting information on the microstructure of plasma polymers from ToF-SIMS measurements.

Dynamic mechanical properties of hydroxyapatite/polyethylene oxide nanocomposites: characterizing isotropic and post-processing microstructures

NASA Astrophysics Data System (ADS)

Shofner, Meisha; Lee, Ji Hoon

2012-02-01

Compatible component interfaces in polymer nanocomposites can be used to facilitate a dispersed morphology and improved physical properties as has been shown extensively in experimental results concerning amorphous matrix nanocomposites. In this research, a block copolymer compatibilized interface is employed in a semi-crystalline matrix to prevent large scale nanoparticle clustering and enable microstructure construction with post-processing drawing. The specific materials used are hydroxyapatite nanoparticles coated with a polyethylene oxide-b-polymethacrylic acid block copolymer and a polyethylene oxide matrix. Two particle shapes are used: spherical and needle-shaped. Characterization of the dynamic mechanical properties indicated that the two nanoparticle systems provided similar levels of reinforcement to the matrix. For the needle-shaped nanoparticles, the post-processing step increased matrix crystallinity and changed the thermomechanical reinforcement trends. These results will be used to further refine the post-processing parameters to achieve a nanocomposite microstructure with triangulated arrays of nanoparticles.

Specific features of direct formation of graphite-like microstructures in polycarbonate samples by single femtosecond laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganin, D V; Lapshin, K E; Obidin, A Z

2015-11-30

We present the result of the experiments on producing graphite-like cylindrical microstructures by focusing single femtosecond laser pulses into the bulk of a transparent polymer (polycarbonate). The microstructures are embedded in a cladding with a modified refractive index, possessing waveguide properties. In the experiments with nontransparent screens and diaphragms, placed in the laser beam in front of the entrance pupil of the objective with a large numerical aperture, we have found that the paraxial rays are blocked by the peripheral ones, which reduces the length of the destruction region in the pre-focal zone. In the experiments with transparent screens andmore » diaphragms, introducing optical delays τ{sub d} between the paraxial and peripheral rays, the quantitative dependence of the destruction region length in the pre-focal zone on the value of τ{sub d} is determined. (interaction of laser radiation with matter. laser plasma)« less

Preparation and Characterization of New Geopolymer-Epoxy Resin Hybrid Mortars

PubMed Central

Colangelo, Francesco; Roviello, Giuseppina; Ricciotti, Laura; Ferone, Claudio; Cioffi, Raffaele

2013-01-01

The preparation and characterization of metakaolin-based geopolymer mortars containing an organic epoxy resin are presented here for the first time. The specimens have been prepared by means of an innovative in situ co-reticulation process, in mild conditions, of commercial epoxy based organic resins and geopolymeric slurry. In this way, geopolymer based hybrid mortars characterized by a different content of normalized sand (up to 66% in weight) and by a homogeneous dispersion of the organic resin have been obtained. Once hardened, these new materials show improved compressive strength and toughness in respect to both the neat geopolymer and the hybrid pastes since the organic polymer provides a more cohesive microstructure, with a reduced amount of microcracks. The microstructural characterization allows to point out the presence of an Interfacial Transition Zone similar to that observed in cement based mortars and concretes. A correlation between microstructural features and mechanical properties has been studied too. PMID:28811418

Optical properties of graphene-based materials in transparent polymer matrices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bayrak, Osman; Demirci, Emrah, E-mail: E.Demirci@lboro.ac.uk; Silberschmidt, Vadim V.

2016-08-22

Different aspects of graphene-based materials (GBMs) and GBM-nanocomposites have been investigated due to their intriguing features; one of these features is their transparency. Transparency of GBMs has been of an interest to scientists and engineers mainly with regard to electronic devices. In this study, optical transmittance of structural, purpose-made nanocomposites reinforced with GBMs was analyzed to lay a foundation for optical microstructural characterization of nanocomposites in future studies. Two main types of GBM reinforcements were studied, graphene oxide (GO) and graphite nanoplates (GNPs). The nanocomposites investigated are GO/poly(vinyl alcohol), GO/sodium alginate, and GNP/epoxy with different volume fractions of GBMs. Togethermore » with UV-visible spectrophotometry, image-processing-assisted micro and macro photography were used to assess the transparency of GBMs embedded in the matrices. The micro and macro photography methods developed were proven to be an alternative way of measuring light transmittance of semi-transparent materials. It was found that there existed a linear relationship between light absorbance and a volume fraction of GBMs embedded in the same type of polymer matrices, provided that the nanocomposites of interest had the same thicknesses. This suggests that the GBM dispersion characteristics in the same type of polymer are similar and any possible change in crystal structure of polymer due to different volumetric contents of GBM does not have an effect on light transmittance of the matrices. The study also showed that the same types of GBMs could display different optical properties in different matrix materials. The results of this study will help to develop practical microstructural characterization techniques for GBM-based nanocomposites.« less

Study on Buckling of Stiff Thin Films on Soft Substrates as Functional Materials

NASA Astrophysics Data System (ADS)

Ma, Teng

In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ˜100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications.

Defects in electro-optically active polymer solids

NASA Technical Reports Server (NTRS)

Martin, David C.

1993-01-01

There is considerable current interest in the application of organic and polymeric materials for electronic and photonic devices. The rapid, non-linear optical (NLO) response of these materials makes them attractive candidates for waveguides, interferometers, and frequency doublers. In order to realize the full potential of these systems, it is necessary to develop processing schemes which can fabricate these molecules into ordered arrangements. There is enormous potential for introducing well-defined, local variations in microstructure to control the photonic properties of organic materials by rational 'defect engineering.' This effort may eventually become as technologically important as the manipulation of the electronic structure of solid-state silicon based devices is at present. The success of this endeavor will require complimentary efforts in the synthesis, processing, and characterization of new materials. Detailed information about local microstructure will be necessary to understand the influence of symmetry breaking of the solid phases near point, line, and planar defects. In metallic and inorganic polycrystalline materials, defects play an important role in modifying macroscopic properties. To understand the influence of particular defects on the properties of materials, it has proven useful to isolate the defect by creating bicrystals between two-component single crystals. In this way the geometry of a grain boundary defect and its effect on macroscopic properties can be determined unambiguously. In crystalline polymers it would be valuable to establish a similar depth of understanding about the relationship between defect structure and macroscopic properties. Conventionally processed crystalline polymers have small crystallites (10-20 nm), which implies a large defect density in the solid state. Although this means that defects may play an important or even dominant role in crystalline or liquid crystalline polymer systems, it also makes it difficult to isolate the effect of a particular boundary on a macroscopically observed property. However, the development of solid-state and thin-film polymerization mechanisms have facilitated the synthesis of highly organized and ordered polymers. These systems provide a unique opportunity to isolate and investigate in detail the structure of covalently bonded solids near defects and the effect of these defects on the properties of the material. The study of defects in solid polymers has been the subject of a recent review (Martin, 1993).

Micro-opto-mechanical devices and systems using epitaxial lift off

NASA Technical Reports Server (NTRS)

Camperi-Ginestet, C.; Kim, Young W.; Wilkinson, S.; Allen, M.; Jokerst, N. M.

1993-01-01

The integration of high quality, single crystal thin film gallium arsenide (GaAs) and indium phosphide (InP) based photonic and electronic materials and devices with host microstructures fabricated from materials such as silicon (Si), glass, and polymers will enable the fabrication of the next generation of micro-opto-mechanical systems (MOMS) and optoelectronic integrated circuits. Thin film semiconductor devices deposited onto arbitrary host substrates and structures create hybrid (more than one material) near-monolithic integrated systems which can be interconnected electrically using standard inexpensive microfabrication techniques such as vacuum metallization and photolithography. These integrated systems take advantage of the optical and electronic properties of compound semiconductor devices while still using host substrate materials such as silicon, polysilicon, glass and polymers in the microstructures. This type of materials optimization for specific tasks creates higher performance systems than those systems which must use trade-offs in device performance to integrate all of the function in a single material system. The low weight of these thin film devices also makes them attractive for integration with micromechanical devices which may have difficulty supporting and translating the full weight of a standard device. These thin film devices and integrated systems will be attractive for applications, however, only when the development of low cost, high yield fabrication and integration techniques makes their use economically feasible. In this paper, we discuss methods for alignment, selective deposition, and interconnection of thin film epitaxial GaAs and InP based devices onto host substrates and host microstructures.

Use of polarized spectroscopy as a tool for examining the microstructure of cellulosic textile fibers.

PubMed

Garside, Paul; Wyeth, Paul

2007-05-01

Textile artifacts form a vital part of our cultural heritage. In order to determine appropriate methods of conservation, storage, and display, it is important to understand the current physical state of an artifact, as effected by the microstructure of the component fibers. The semi-crystalline nature of the constituent polymer aggregates, the degree of crystallinity, and the crystallite orientation have a significant influence on mechanical properties. The value of polarized Fourier transform infrared (FT-IR) spectroscopy in probing these aspects of cellulosic fibers has been assessed. A variety of representative fibers (both natural plant fibers and regenerated materials) were examined by polarized attenuated total reflection spectroscopy (Pol-ATR) and polarized infrared microspectroscopy (Pol-microIR); the former is a surface sampling technique and the latter is a transmission technique. The introduction of a polarizer into the system allows the alignment as well as the nature of bonds to be determined, and thus the presence and extent of crystallinity or long range ordering can be investigated. Using the data from the Pol-ATR experiments, it was found to be possible to derive the principle alignment of the cellulose polymer with respect to the fiber axis, along with an indication of the total cellulose crystallinity of the material, as measured by a crystallinity parameter, Chi. The Pol-microIR spectra, on the other hand, yielded more limited information, particularly when considering plant fibers with more complex microstructures.

Fabrication of 3D gold/polymer conductive microstructures via direct laser writing (Conference Presentation)

NASA Astrophysics Data System (ADS)

Blasco, Eva; Müller, Jonathan B.; Müller, Patrick; Fischer, Andreas C.; Barner-Kowollik, Christopher; Wegener, Martin

2017-02-01

During the last years there has been significant interest in the fabrication of conductive three-dimensional (3D) structures on the micrometer scale due to their potential applications in microelectronics or emerging fields such as flexible electronics, nanophotonics, and plasmonics. Two-photon direct laser writing (DLW) has been proposed as a potential tool for the fabrication of 3D microstructures in various contexts. The majority of these two-photon processes involve the preparation of insoluble polymeric networks using photopolymerizable photoresins based on acrylate or epoxy groups. Nevertheless, the preparation of conductive 3D microstructures is still very challenging. The aim of the current work has been the preparation of conductive 3D microstructures via DLW by employing a newly developed photoresist. The photoresist consists of acrylate-functionalized poly(ethylene glycol) derivates and HAuCl4 as the gold precursor. By varying the gold content of the photoresist, different structures have been prepared and characterized by SEM and XPS. Conductivity of individual wires between prefabricated macroelectrodes has been measured too. Subsequently, the material has been employed to demonstrate the possibility of true 3D microscale connections.

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures

DOE PAGES

Cummings, John; Lowengrub, John S.; Sumpter, Bobby G.; ...

2018-02-09

Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this paper, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for themore » derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Finally, effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.« less

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cummings, John; Lowengrub, John S.; Sumpter, Bobby G.

Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this paper, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for themore » derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Finally, effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.« less

Three-Dimensional-Moldable Nanofiber-Reinforced Transparent Composites with a Hierarchically Self-Assembled "Reverse" Nacre-like Architecture.

PubMed

Biswas, Subir K; Sano, Hironari; Shams, Md Iftekhar; Yano, Hiroyuki

2017-09-06

Achieving a structural hierarchy and a uniform nanofiller dispersion simultaneously remains highly challenging for obtaining a robust polymer nanocomposite of immiscible components. In this study, a remarkably facile Pickering emulsification approach is developed to fabricate hierarchical composites of immiscible acrylic polymer and native cellulose nanofibers by taking advantage of the dual role of the nanofibers as both emulsion stabilizer and polymer reinforcement. The composites feature a unique "reverse" nacre-like microstructure reinforced with a well-dispersed two-tier hierarchical nanofiber network, leading to a synergistic high strength, modulus, and toughness (20, 50, and 53 times that of neat polymer, respectively), high optical transparency (89%), high flexibility, and a drastically low thermal expansion (13 ppm K -1 , 1/15th of the neat polymer). The nanocomposites have a three-dimensional-shape moldability, also their surface can be patterned with micro/nanoscale features with high fidelity by in situ compression molding, making them attractive as the substrate for flexible displays, smart contact lens devices, and photovoltaics. The Pickering emulsification approach should be broadly applicable for the fabrication of novel functional materials of various immiscible components.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope.

PubMed

Bäcke, Olof; Lindqvist, Camilla; de Zerio Mendaza, Amaia Diaz; Gustafsson, Stefan; Wang, Ergang; Andersson, Mats R; Müller, Christian; Kristiansen, Per Magnus; Olsson, Eva

2017-05-01

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV-vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope.

PubMed

Bäcke, Olof; Lindqvist, Camilla; de Zerio Mendaza, Amaia Diaz; Gustafsson, Stefan; Wang, Ergang; Andersson, Mats R; Müller, Christian; Kristiansen, Per Magnus; Olsson, Eva

2017-02-01

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV-vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrohydrodynamic pressure enhanced by free space charge for electrically induced structure formation with high aspect ratio.

PubMed

Tian, Hongmiao; Wang, Chunhui; Shao, Jinyou; Ding, Yucheng; Li, Xiangming

2014-10-28

Electrically induced structure formation (EISF) is an interesting and unique approach for generating a microstructured duplicate from a rheological polymer by a spatially modulated electric field induced by a patterned template. Most of the research on EISF have so far used various dielectric polymers (with an electrical conductivity smaller than 10(-10) S/m that can be considered a perfect dielectric), on which the electric field induces a Maxwell stress only due to the dipoles (or bounded charges) in the polymer molecules, leading to a structure with a small aspect ratio. This paper presents a different approach for improving the aspect ratio allowed in EISF by doping organic salt into the perfect dielectric polymer, i.e., turning the perfect dielectric into a leaky dielectric, considering the fact that the free space charges enriched in the leaky dielectric polymer can make an additional contribution to the Maxwell stress, i.e., electrohydrodynamic pressure, which is desirable for high aspect ratio structuring. Our numerical simulations and experimental tests have shown that a leaky dielectric polymer, with a small conductivity comparable to that of deionized water, can be much more effective at being electrohydrodynamically deformed into a high aspect ratio in comparison with a perfect dielectric polymer when both of them have roughly the same dielectric constant.

A Mechanistic Understanding of a Binary Additive System to Synergistically Boost Efficiency in All-Polymer Solar Cells

PubMed Central

Kim, Yu Jin; Ahn, Sunyong; Wang, Dong Hwan; Park, Chan Eon

2015-01-01

All-polymer solar cells are herein presented utilizing the PBDTTT-CT donor and the P(NDI2OD-T2) acceptor with 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) binary solvent additives. A systematic study of the polymer/polymer bulk heterojunction photovoltaic cells processed from the binary additives revealed that the microstructures and photophysics were quite different from those of a pristine system. The combination of DIO and CN with a DIO/CN ratio of 3:1 (3 vol% DIO, 1 vol% CN and 96 vol% o-DCB) led to suitable penetrating polymer networks, efficient charge generation and balanced charge transport, which were all beneficial to improving the efficiency. This improvement is attributed to increase in power conversion efficiency from 2.81% for a device without additives to 4.39% for a device with the binary processing additives. A detailed investigation indicates that the changes in the polymer:polymer interactions resulted in the formation of a percolating nasnoscale morphology upon processing with the binary additives. Depth profile measurements with a two-dimensional grazing incidence wide-angle X-ray scattering confirm this optimum phase feature. Furthermore impedance spectroscopy also finds evidence for synergistically boosting the device performance. PMID:26658472

A predictive machine learning approach for microstructure optimization and materials design

NASA Astrophysics Data System (ADS)

Liu, Ruoqian; Kumar, Abhishek; Chen, Zhengzhang; Agrawal, Ankit; Sundararaghavan, Veera; Choudhary, Alok

2015-06-01

This paper addresses an important materials engineering question: How can one identify the complete space (or as much of it as possible) of microstructures that are theoretically predicted to yield the desired combination of properties demanded by a selected application? We present a problem involving design of magnetoelastic Fe-Ga alloy microstructure for enhanced elastic, plastic and magnetostrictive properties. While theoretical models for computing properties given the microstructure are known for this alloy, inversion of these relationships to obtain microstructures that lead to desired properties is challenging, primarily due to the high dimensionality of microstructure space, multi-objective design requirement and non-uniqueness of solutions. These challenges render traditional search-based optimization methods incompetent in terms of both searching efficiency and result optimality. In this paper, a route to address these challenges using a machine learning methodology is proposed. A systematic framework consisting of random data generation, feature selection and classification algorithms is developed. Experiments with five design problems that involve identification of microstructures that satisfy both linear and nonlinear property constraints show that our framework outperforms traditional optimization methods with the average running time reduced by as much as 80% and with optimality that would not be achieved otherwise.

Towards ultraporous poly(L-lactide) scaffolds from quaternary immiscible polymer blends.

PubMed

Virgilio, N; Sarazin, P; Favis, B D

2010-08-01

Ultraporous poly(l-lactide) (PLLA) scaffolds were prepared by melt-processing quaternary ethylene propylene diene rubber/poly(epsilon-caprolactone)/polystyrene/poly(l-lactide) (EPDM/PCL/PS/PLLA) 45/45/5/5 %vol. polymer blends modified with a PS-b-PLLA diblock copolymer. The morphology consists of a PS+PLLA+copolymer sub-blend layer forming at the interface of the EPDM and PCL phases. Quiescent annealing and interfacial modification using the block copolymer are used to control the blend microstructure. The ultraporous structure is subsequently obtained by selectively extracting the EPDM, PS and PCL phases. The PLLA scaffolds modified with the PS-b-PLLA copolymer present themselves as fully interconnected porous networks with asymmetric channel walls, one side being smooth while the other is covered with an array of submicron-sized PLLA droplets. They are prepared with a high degree of control over the pore size, with averages ranging from 5microm to over 100microm and a specific surface from 9.1 to 23.1m(2)/g of PLLA, as annealing is carried out from 0 to 60min. The void volume reaches values as high as 95% and in all cases the shape and dimensions of the scaffolds are maintained with a high level of integrity. The proposed method represents a comprehensive approach towards the design and generation of porous PLLA scaffolds based on complex morphologies from melt-processed multiphase polymer systems. Copyright 2010 Elsevier Ltd. All rights reserved.

Tailored synthesis of monodispersed nano/submicron porous silicon oxycarbide (SiOC) spheres with improved Li-storage performance as an anode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Shi, Huimin; Yuan, Anbao; Xu, Jiaqiang

2017-10-01

A spherical silicon oxycarbide (SiOC) material (monodispersed nano/submicron porous SiOC spheres) is successfully synthesized via a specially designed synthetic strategy involving pyrolysis of phenyltriethoxysilane derived pre-ceramic polymer spheres at 900 °C. In order to prevent sintering of the pre-ceramic polymer spheres upon heating, a given amount of hollow porous SiO2 nanobelts which are separately prepared from tetraethyl orthosilicate with CuO nanobelts as templates are introduced into the pre-ceramic polymer spheres before pyrolysis. This material is investigated as an anode for lithium-ion batteries in comparison with the large-size bulk SiOC material synthesized under the similar conditions but without hollow SiO2 nanobelts. The maximum reversible specific capacity of ca. 900 mAh g-1 is delivered at the current density of 100 mA g-1 and ca. 98% of the initial capacity is remained after 100 cycles at 100 mA g-1 for the SiOC spheres material, which are much superior to the bulk SiOC material. The improved lithium storage performance in terms of specific capacity and cyclability is attributed to its particular morphology of monodisperse nano/submicron porous spheres as well as its modified composition and microstructure. This SiOC material has higher Li-storage activity and better stability against volume expansion during repeated lithiation and delithiation cycling.

Adaptive, Active and Multifunctional Composite and Hybrid Materials Program: Composite and Hybrid Materials ERA

DTIC Science & Technology

2014-04-01

Microvascular Self - Healing Composites Mechanical Evaluation ................................................................................11...Thermoplastic SMP Foam Microstructure- Mechanical Stress-Strain Relationships 2.2.2 Microvascular Self - Healing Composites Mechanical Evaluation 2.3.1 Z...materials, and embedded sensory and circulatory systems. Damage repair of torn or injured tissue was demonstrated by the use of self - healing polymer

Real-time Analysis of the Enzymatic Biodegradation of Polyhydroxyalkanoate Thin Films Using Microfabricated Polymer Microstructures

NASA Astrophysics Data System (ADS)

Delfaus, Stephen; Latuga, Brian M.; Morse, Clinton; McCarney, Evan R.; Rossini, Connie J.; Augustine, Brian H.; Flythe, Michael D.; Rowe, Sean; Baron, Stephen F.; Dennis, Douglas E.

2003-11-01

In-situ atomic force microscopy (AFM) allows for the real-time acquisition and analysis of materials undergoing biological and chemical alterations. A co-polymer blend of poly 3-hydroxybutyrate / poly 3-hydroxyvalerate P(3HB-3HV) were spun-cast onto glass slides to create thin films with film thickness of 40 nm. This polymer is naturally biodegradable by a variety of bacterially produced enzymes. In this study, these materials were degraded by an untyped and concentrated Strptomyces sp. enzyme produced from soil. Using liquid-cell AFM in contact mode, we were able to observe biodegradation uniformly across the surface of the P(3HB-3HV) films beginning within 2 min of introduction of the enzyme. Height standards have been developed using microcontact printing of self assembled monolayers and selective dewetting to produce P(3HB-3HV) structures with dimensions as small as 10 mm. We will discuss the use of microfabricated height standards to measure biodegradation kinetics in these polymers.

Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Pater, Ruth H.; Eftekhari, Abe

1996-01-01

Thermoset and thermoplastic polyimides have complementary physical and mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. A combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPN) of thermoset LaRC(TM)-RP46 and thermoplastic LaRC(TM)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0:100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical and mechanical properties. As expected, positronium atoms are not formed in these samples. The second lifetime component has been used to infer the positron trap dimensions. The 'free volume' goes through a minimum at a ratio of about 50:50, and this suggests that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples are discussed.

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE PAGES

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; ...

2017-11-30

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers

PubMed Central

Botiz, Ioan; Stingelin, Natalie

2014-01-01

It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties. PMID:28788568

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Self-assembly of free-standing RNA membranes

NASA Astrophysics Data System (ADS)

Han, Daehoon; Park, Yongkuk; Kim, Hyejin; Lee, Jong Bum

2014-07-01

RNA has emerged as a promising material for nanostructure and microstructure engineering. Although rare, some macroscopic RNA structures have also been constructed using lipid or polymer materials. Here, we report the first example of an enzymatically generated RNA membrane. This robust and free-standing RNA membrane has a macroscopic structure and is generated without any polymer support or complexation. Our RNA membrane is fabricated following two sequential processes, complementary rolling circle transcription and evaporation-induced self-assembly, and its structural and functional properties are rationally controlled by adjusting RNA base pairing. In this study, three types of RNA membranes are fabricated and are used to demonstrate potential applications.

Detection of percolating paths in polyhedral segregated network composites using electrostatic force microscopy and conductive atomic force microscopy

NASA Astrophysics Data System (ADS)

Waddell, J.; Ou, R.; Capozzi, C. J.; Gupta, S.; Parker, C. A.; Gerhardt, R. A.; Seal, K.; Kalinin, S. V.; Baddorf, A. P.

2009-12-01

Composite specimens possessing polyhedral segregated network microstructures require a very small amount of nanosize filler, <1 vol %, to reach percolation because percolation occurs by accumulation of the fillers along the edges of the deformed polymer matrix particles. In this paper, electrostatic force microscopy (EFM) and conductive atomic force microscopy (C-AFM) were used to confirm the location of the nanosize fillers and the corresponding percolating paths in polymethyl methacrylate/carbon black composites. The EFM and C-AFM images revealed that the polyhedral polymer particles were coated with filler, primarily on the edges as predicted by the geometric models provided.

Preparation and analysis of multilayer composites based on polyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.; Baklagina, Yu. G.; Romanov, D. P.; Kononova, S. V.; Volod'ko, A. V.; Ermak, I. M.; Klechkovskaya, V. V.; Skorik, Yu. A.

2016-11-01

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan-hyaluronic acid, chitosan-alginic acid, and chitosan-carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Excellent lubricating behavior of Brasenia schreberi mucilage.

PubMed

Li, Jinjin; Liu, Yuhong; Luo, Jianbin; Liu, Pengxiao; Zhang, Chenhui

2012-05-22

The present work reports an excellent lubrication property of an aquatic plant called Brasenia schreberi (BS). To investigate the lubrication characteristics of the BS mucilage, a novel measuring system is designed, and an ultralow friction coefficient about 0.005 between the mucilage and glass surface has been obtained. It is found that the ultralow friction is closely related to the structure of mucilage and water molecules in the mucilage. The microstructure analysis indicates that the mucilage surrounding BS forms a kind of polysaccharide gel with many nanosheets. A possible lubrication mechanism is proposed that the formation of hydration layers among these polymer nanosheets with plenty of bonded water molecules causes the ultralow friction. The excellent lubrication property has a potential application for reducing the friction between a glossy pill coated with such layer of mucilage and people's throats.

Rotational 3D printing of damage-tolerant composites with programmable mechanics

PubMed Central

Raney, Jordan R.; Compton, Brett G.; Ober, Thomas J.; Shea, Kristina; Lewis, Jennifer A.

2018-01-01

Natural composites exhibit exceptional mechanical performance that often arises from complex fiber arrangements within continuous matrices. Inspired by these natural systems, we developed a rotational 3D printing method that enables spatially controlled orientation of short fibers in polymer matrices solely by varying the nozzle rotation speed relative to the printing speed. Using this method, we fabricated carbon fiber–epoxy composites composed of volume elements (voxels) with programmably defined fiber arrangements, including adjacent regions with orthogonally and helically oriented fibers that lead to nonuniform strain and failure as well as those with purely helical fiber orientations akin to natural composites that exhibit enhanced damage tolerance. Our approach broadens the design, microstructural complexity, and performance space for fiber-reinforced composites through site-specific optimization of their fiber orientation, strain, failure, and damage tolerance. PMID:29348206

Ultrathin high-resolution flexographic printing using nanoporous stamps

PubMed Central

Kim, Sanha; Sojoudi, Hossein; Zhao, Hangbo; Mariappan, Dhanushkodi; McKinley, Gareth H.; Gleason, Karen K.; Hart, A. John

2016-01-01

Since its invention in ancient times, relief printing, commonly called flexography, has been used to mass-produce artifacts ranging from decorative graphics to printed media. Now, higher-resolution flexography is essential to manufacturing low-cost, large-area printed electronics. However, because of contact-mediated liquid instabilities and spreading, the resolution of flexographic printing using elastomeric stamps is limited to tens of micrometers. We introduce engineered nanoporous microstructures, comprising polymer-coated aligned carbon nanotubes (CNTs), as a next-generation stamp material. We design and engineer the highly porous microstructures to be wetted by colloidal inks and to transfer a thin layer to a target substrate upon brief contact. We demonstrate printing of diverse micrometer-scale patterns of a variety of functional nanoparticle inks, including Ag, ZnO, WO3, and CdSe/ZnS, onto both rigid and compliant substrates. The printed patterns have highly uniform nanoscale thickness (5 to 50 nm) and match the stamp features with high fidelity (edge roughness, ~0.2 μm). We derive conditions for uniform printing based on nanoscale contact mechanics, characterize printed Ag lines and transparent conductors, and achieve continuous printing at a speed of 0.2 m/s. The latter represents a combination of resolution and throughput that far surpasses industrial printing technologies. PMID:27957542

Manufacturing of three-dimensionally microstructured nanocomposites through microfluidic infiltration.

PubMed

Dermanaki-Farahani, Rouhollah; Lebel, Louis Laberge; Therriault, Daniel

2014-03-12

Microstructured composite beams reinforced with complex three-dimensionally (3D) patterned nanocomposite microfilaments are fabricated via nanocomposite infiltration of 3D interconnected microfluidic networks. The manufacturing of the reinforced beams begins with the fabrication of microfluidic networks, which involves layer-by-layer deposition of fugitive ink filaments using a dispensing robot, filling the empty space between filaments using a low viscosity resin, curing the resin and finally removing the ink. Self-supported 3D structures with other geometries and many layers (e.g. a few hundreds layers) could be built using this method. The resulting tubular microfluidic networks are then infiltrated with thermosetting nanocomposite suspensions containing nanofillers (e.g. single-walled carbon nanotubes), and subsequently cured. The infiltration is done by applying a pressure gradient between two ends of the empty network (either by applying a vacuum or vacuum-assisted microinjection). Prior to the infiltration, the nanocomposite suspensions are prepared by dispersing nanofillers into polymer matrices using ultrasonication and three-roll mixing methods. The nanocomposites (i.e. materials infiltrated) are then solidified under UV exposure/heat cure, resulting in a 3D-reinforced composite structure. The technique presented here enables the design of functional nanocomposite macroscopic products for microengineering applications such as actuators and sensors.

Manufacturing of Three-dimensionally Microstructured Nanocomposites through Microfluidic Infiltration

PubMed Central

Dermanaki-Farahani, Rouhollah; Lebel, Louis Laberge; Therriault, Daniel

2014-01-01

Microstructured composite beams reinforced with complex three-dimensionally (3D) patterned nanocomposite microfilaments are fabricated via nanocomposite infiltration of 3D interconnected microfluidic networks. The manufacturing of the reinforced beams begins with the fabrication of microfluidic networks, which involves layer-by-layer deposition of fugitive ink filaments using a dispensing robot, filling the empty space between filaments using a low viscosity resin, curing the resin and finally removing the ink. Self-supported 3D structures with other geometries and many layers (e.g. a few hundreds layers) could be built using this method. The resulting tubular microfluidic networks are then infiltrated with thermosetting nanocomposite suspensions containing nanofillers (e.g. single-walled carbon nanotubes), and subsequently cured. The infiltration is done by applying a pressure gradient between two ends of the empty network (either by applying a vacuum or vacuum-assisted microinjection). Prior to the infiltration, the nanocomposite suspensions are prepared by dispersing nanofillers into polymer matrices using ultrasonication and three-roll mixing methods. The nanocomposites (i.e. materials infiltrated) are then solidified under UV exposure/heat cure, resulting in a 3D-reinforced composite structure. The technique presented here enables the design of functional nanocomposite macroscopic products for microengineering applications such as actuators and sensors. PMID:24686754

Nanostructured Drugs Embedded into a Polymeric Matrix: Vinpocetine/PVP Hybrids Investigated by Debye Function Analysis.

PubMed

Hasa, Dritan; Giacobbe, Carlotta; Perissutti, Beatrice; Voinovich, Dario; Grassi, Mario; Cervellino, Antonio; Masciocchi, Norberto; Guagliardi, Antonietta

2016-09-06

Microcrystalline vinpocetine, coground with cross-linked polyvinylpyrrolidone, affords hybrids containing nanosized drug nanocrystals, the size and size distributions of which depend on milling times and drug-to-polymer weight ratios. Using an innovative approach to microstructural characterization, we analyzed wide-angle X-ray total scattering data by the Debye function analysis and demonstrated the possibility to characterize pharmaceutical solid dispersions obtaining a reliable quantitative view of the physicochemical status of the drug dispersed in an amorphous carrier. The microstructural properties derived therefrom have been successfully employed in reconciling the enigmatic difference in behavior between in vitro and in vivo solubility tests performed on nanosized vinpocetine embedded in a polymeric matrix.

Dynamic 3D strain measurements with embedded micro-structured optical fiber Bragg grating sensors during impact on a CFRP coupon

NASA Astrophysics Data System (ADS)

Goossens, Sidney; Geernaert, Thomas; De Pauw, Ben; Lamberti, Alfredo; Vanlanduit, Steve; Luyckx, Geert; Chiesura, Gabriele; Thienpont, Hugo; Berghmans, Francis

2017-04-01

Composite materials are increasingly used in aerospace applications, owing to their high strength-to-mass ratio. Such materials are nevertheless vulnerable to impact damage. It is therefore important to investigate the effects of impacts on composites. Here we embed specialty microstructured optical fiber Bragg grating based sensors inside a carbon fiber reinforced polymer, providing access to the 3D strain evolution within the composite during impact. We measured a maximum strain of -655 μɛ along the direction of impact, and substantially lower values in the two in-plane directions. Such in-situ characterization can trigger insight in the development of impact damage in composites.

Surface modification of SU8 photoresist for shrinkage improvement in a monolithic MEMS microstructure

NASA Astrophysics Data System (ADS)

Chung, C. K.; Hong, Y. Z.

2007-02-01

The effect of O2 plasma treatment on the surface property of exposed and unexposed SU8 photoresist has been investigated for the fabrication of a monolithic MEMS microstructure. It can solve the non-uniformity problem of second resist coating on the SU8 with high intrinsic shrinkage after exposure and post-exposure baking (PEB) in the fabrication of the stacked polymer-metal or polymer-polymer structure, which was used in the application of microfluid, bio and chemistry. The thickness difference of untreated SU8 before PEB between the exposed and unexposed SU8 was about 0.3% while that after PEB increased to about 6%. It could result in large non-uniformity of about 18 µm thickness difference for the following second resist coating on the hydrophobic surface without plasma treatment. The surface property of SU8 in terms of the contact angle and surface energy can be adjusted by O2 plasma treatment for enhancing the coating uniformity of the following resist. The measured contact angles of the exposed and unexposed SU8 decrease with O2 plasma time, corresponding to the increased surface energy determined by the Lifshitz-van der Waals/Lewis acid-base approach. It displayed that the similar hydrophilic surface property can minimize the thickness difference of second resist coating on the first shrunken SU8. A monolithic nozzle plate with a physical resolution of 600 dpi in a single column was demonstrated for an inkjet application based on the improved uniformity.

Creep resistance. [of high temperature alloys

NASA Technical Reports Server (NTRS)

Tien, J. K.; Malu, M.; Purushothaman, S.

1976-01-01

High-temperature structural applications usually require creep resistance because some average stress is maintained for prolonged periods. Alloy and microstructural design guidelines for creep resistance are presented through established knowledge on creep behavior and its functional dependences on alloy microstructure. Important considerations related to creep resistance of alloys as well as those that are harmful to high-temperature properties are examined. Although most of the creep models do not predict observed creep behavior quantitatively, they are sophisticated enough to provide alloy or microstructural design guidelines. It is shown that creep-resistant microstructures are usually in conflict with microstructures that improve such other properties as stress rupture ductility. Greater understanding of the effects of environments on creep and stress rupture behavior of materials is necessary before one can optimally design alloys for applications in different environments.

From Artisanal to CAD-CAM Blocks: State of the Art of Indirect Composites.

PubMed

Mainjot, A K; Dupont, N M; Oudkerk, J C; Dewael, T Y; Sadoun, M J

2016-05-01

Indirect composites have been undergoing an impressive evolution over the last few years. Specifically, recent developments in computer-aided design-computer-aided manufacturing (CAD-CAM) blocks have been associated with new polymerization modes, innovative microstructures, and different compositions. All these recent breakthroughs have introduced important gaps among the properties of the different materials. This critical state-of-the-art review analyzes the strengths and weaknesses of the different varieties of CAD-CAM composite materials, especially as compared with direct and artisanal indirect composites. Indeed, new polymerization modes used for CAD-CAM blocks-especially high temperature (HT) and, most of all, high temperature-high pressure (HT-HP)-are shown to significantly increase the degree of conversion in comparison with light-cured composites. Industrial processes also allow for the augmentation of the filler content and for the realization of more homogeneous structures with fewer flaws. In addition, due to their increased degree of conversion and their different monomer composition, some CAD-CAM blocks are more advantageous in terms of toxicity and monomer release. Finally, materials with a polymer-infiltrated ceramic network (PICN) microstructure exhibit higher flexural strength and a more favorable elasticity modulus than materials with a dispersed filler microstructure. Consequently, some high-performance composite CAD-CAM blocks-particularly experimental PICNs-can now rival glass-ceramics, such as lithium-disilicate glass-ceramics, for use as bonded partial restorations and crowns on natural teeth and implants. Being able to be manufactured in very low thicknesses, they offer the possibility of developing innovative minimally invasive treatment strategies, such as "no prep" treatment of worn dentition. Current issues are related to the study of bonding and wear properties of the different varieties of CAD-CAM composites. There is also a crucial need to conduct clinical studies. Last, manufacturers should provide more complete information regarding their product polymerization process, microstructure, and composition, which significantly influence CAD-CAM material properties. © International & American Associations for Dental Research 2016.

An efficient algorithm for generating diverse microstructure sets and delineating properties closures

DOE PAGES

Johnson, Oliver K.; Kurniawan, Christian

2018-02-03

Properties closures delineate the theoretical objective space for materials design problems, allowing designers to make informed trade-offs between competing constraints and target properties. In this paper, we present a new algorithm called hierarchical simplex sampling (HSS) that approximates properties closures more efficiently and faithfully than traditional optimization based approaches. By construction, HSS generates samples of microstructure statistics that span the corresponding microstructure hull. As a result, we also find that HSS can be coupled with synthetic polycrystal generation software to generate diverse sets of microstructures for subsequent mesoscale simulations. Finally, by more broadly sampling the space of possible microstructures, itmore » is anticipated that such diverse microstructure sets will expand our understanding of the influence of microstructure on macroscale effective properties and inform the construction of higher-fidelity mesoscale structure-property models.« less

An efficient algorithm for generating diverse microstructure sets and delineating properties closures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Oliver K.; Kurniawan, Christian

Properties closures delineate the theoretical objective space for materials design problems, allowing designers to make informed trade-offs between competing constraints and target properties. In this paper, we present a new algorithm called hierarchical simplex sampling (HSS) that approximates properties closures more efficiently and faithfully than traditional optimization based approaches. By construction, HSS generates samples of microstructure statistics that span the corresponding microstructure hull. As a result, we also find that HSS can be coupled with synthetic polycrystal generation software to generate diverse sets of microstructures for subsequent mesoscale simulations. Finally, by more broadly sampling the space of possible microstructures, itmore » is anticipated that such diverse microstructure sets will expand our understanding of the influence of microstructure on macroscale effective properties and inform the construction of higher-fidelity mesoscale structure-property models.« less

A predictive machine learning approach for microstructure optimization and materials design

DOE PAGES

Liu, Ruoqian; Kumar, Abhishek; Chen, Zhengzhang; ...

2015-06-23

This paper addresses an important materials engineering question: How can one identify the complete space (or as much of it as possible) of microstructures that are theoretically predicted to yield the desired combination of properties demanded by a selected application? We present a problem involving design of magnetoelastic Fe-Ga alloy microstructure for enhanced elastic, plastic and magnetostrictive properties. While theoretical models for computing properties given the microstructure are known for this alloy, inversion of these relationships to obtain microstructures that lead to desired properties is challenging, primarily due to the high dimensionality of microstructure space, multi-objective design requirement and non-uniquenessmore » of solutions. These challenges render traditional search-based optimization methods incompetent in terms of both searching efficiency and result optimality. In this paper, a route to address these challenges using a machine learning methodology is proposed. A systematic framework consisting of random data generation, feature selection and classification algorithms is developed. In conclusion, experiments with five design problems that involve identification of microstructures that satisfy both linear and nonlinear property constraints show that our framework outperforms traditional optimization methods with the average running time reduced by as much as 80% and with optimality that would not be achieved otherwise.« less

Thermal spraying of polyethylene-based polymers: Processing and characterization

NASA Astrophysics Data System (ADS)

Otterson, David Mark

This research explores the development of a flame-spray process map as it relates to polymers. This work provides a more complete understanding of the thermal history of the coating material from injection, to deposition and finally to cooling. This was accomplished through precise control of the processing conditions during deposition. Mass flow meters were used to monitor air and fuel flows as they were systematically changed, while temperatures were simultaneously monitored along the length of the flame. A process model was then implemented that incorporated this information along with measured particle velocities, particle size distribution, the polymer's melting temperature and its enthalpy of melting. This computational model was then used to develop a process map that described particle softening, melting and decomposition phenomena as a function of particle size and standoff distance. It demonstrated that changes in particle size caused significant variations in particle states achieved in-flight. A series of experiments were used to determine the range of spray parameters within which a cohesive coating without visible signs of degradation could be sprayed. These results provided additional information that complimented the computational processing map. The boundaries established by these results were the basis for a Statistical Design of Experiments that tested the effects that subtle processing changes had on coating properties. A series of processing maps were developed that combined the computational and the experimental results to describe the manner in which processing parameters interact to determine the degree of melting, polymer degradation and coating porosity. Strong interactions between standoff distance and traverse rate can cause the polymer to degrade and form pores in the coating. A clear picture of the manner in which particle size and standoff distance interact to determine particle melting was provided by combining the computational processing map with the collected splats and microstructures. Finally, a strong interaction was observed between standoff distance and flame length, which is determined by the air:fuel ratio. When flame length exceeds the standoff distance, polymer degradation results from excessive heating of the substrate. A descriptive model of the process is then provided to highlight the importance of these interactions. (Abstract shortened by UMI.)

Microstructure investigation on micropore formation in microporous silica materials prepared via a catalytic sol-gel process by small angle X-ray scattering.

PubMed

Shimizu, Wataru; Hokka, Junsuke; Sato, Takaaki; Usami, Hisanao; Murakami, Yasushi

2011-08-04

The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores. This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate (TMOS) using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone (HA) catalyst. Small angle X-ray scattering (SAXS), nitrogen adsorption porosimetry, and transmission electron microscope (TEM) allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols (methanol or ethanol) in the precursor solution, polymer-like aggregates having microscopic correlation length (or mesh-size) < 2 nm and low fractal dimensions ∼2, which is identical to that of an ideal coil polymer, can selectively be synthesized, yielding the uniform micropores with diameters <2 nm in the solid materials. In contrast, the absence of HA or substitution of 1-propanol led to considerably different scattering behavior reflecting the particle-like aggregate formation in the precursor solution, which resulted in the formation of mesopores (diameter >2 nm) in the solid product due to apertures between the particle-like aggregates. The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and their successful imprint on the solid product. The result offers a general but significantly efficient route to creating precisely designed fine porous silica materials under mild condition that serve as low refractive index and efficient thermal insulation materials in their practical applications.

Symposium II: Mechanochemistry in Materials Science, MRS Fall Meeting, Nov 30-Dec 4, 2009, Boston, MA

DTIC Science & Technology

2010-09-02

Dynamic Mechanical Analysis (DMA). The fracture behavior of the mechanophore-linked polymer is also examined through the Double Cleavage Drilled ...multinary complex structures. Structural, microstructural, and chemical characterizations were explored by metrological tools to support this...simple hydrocarbons in order to quantitatively define structure-property relationships for reacting materials under shock compression. Embedded gauge

Microdesigning of Lightweight/High Strength Ceramic Materials

DTIC Science & Technology

1989-07-31

Continue on reverse if necessary and identiy by block number) FIELD GROUP SUB- GROUP Ceramics, Composite Materials, Colloidal Processing Iii 19. ABSTRACT...to identify key processing parameters that affect the microstructure of the composite material. The second section describes experimental results in...results of the significant theoretical effort made in our group . Theoretical models of particle-particle interaction, particle-polymer interaction

Comparison between Cellulose Nanocrystal and Cellulose Nanofibril Reinforced Poly(ethylene oxide) Nanofibers and Their Novel Shish-Kebab-Like Crystalline Structures

Treesearch

Xuezhu Xu; Haoran Wang; Long Jiang; Xinnan Wang; Scott A. Payne; J.Y. Zhu; Ruipeng Li

2014-01-01

Poly(ethylene oxide) (PEO) nanofiber mats were produced by electrospinning. Biobased cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) as reinforcement nanofillers were also added to the polymer to produce composite nanofiber mats. The effects of the two cellulose nanofillers on the rheological properties of the PEO solutions and the microstructure,...

An Experimental Study in the Mechanical Response of Polymer Modified Geopolymers

DTIC Science & Technology

2012-04-01

Compressive and Bending Strength of Fly ash Geopolymers ... 22 LIST OF TABLES Page Table 1. Chemical Composition of Aluminosilicates in Mass... geopolymer matrix composites .” Ceramic Transactions, 153, 227-250. 3. Davidovits J., 1991. “ Geopolymers , inorganic polymeric materials.” Journal of...Understanding the relationship between geopolymer composition , microstructure and mechanical properties.” Colloids and Surfaces.A, Physicochemical

Oxygen ion implantation induced microstructural changes and electrical conductivity in Bakelite RPC detector material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, K. V. Aneesh, E-mail: aneesh1098@gmail.com; Ravikumar, H. B., E-mail: hbr@physics.uni-mysore.ac.in; Ranganathaiah, C., E-mail: cr@physics.uni-mysore.ac.in

2016-05-06

In order to explore the structural modification induced electrical conductivity, samples of Bakelite Resistive Plate Chamber (RPC) detector materials were exposed to 100 keV Oxygen ion in the fluences of 10{sup 12}, 10{sup 13}, 10{sup 14} and 10{sup 15} ions/cm{sup 2}. Ion implantation induced microstructural changes have been studied using Positron Annihilation Lifetime Spectroscopy (PALS) and X-Ray Diffraction (XRD) techniques. Positron lifetime parameters viz., o-Ps lifetime and its intensity shows the deposition of high energy interior track and chain scission leads to the formation of radicals, secondary ions and electrons at lower ion implantation fluences (10{sup 12} to10{sup 14} ions/cm{supmore » 2}) followed by cross-linking at 10{sup 15} ions/cm{sup 2} fluence due to the radical reactions. The reduction in electrical conductivity of Bakelite detector material is correlated to the conducting pathways and cross-links in the polymer matrix. The appropriate implantation energy and fluence of Oxygen ion on polymer based Bakelite RPC detector material may reduce the leakage current, improves the efficiency, time resolution and thereby rectify the aging crisis of the RPC detectors.« less

Computational analysis of particle reinforced viscoelastic polymer nanocomposites - statistical study of representative volume element

NASA Astrophysics Data System (ADS)

Hu, Anqi; Li, Xiaolin; Ajdari, Amin; Jiang, Bing; Burkhart, Craig; Chen, Wei; Brinson, L. Catherine

2018-05-01

The concept of representative volume element (RVE) is widely used to determine the effective material properties of random heterogeneous materials. In the present work, the RVE is investigated for the viscoelastic response of particle-reinforced polymer nanocomposites in the frequency domain. The smallest RVE size and the minimum number of realizations at a given volume size for both structural and mechanical properties are determined for a given precision using the concept of margin of error. It is concluded that using the mean of many realizations of a small RVE instead of a single large RVE can retain the desired precision of a result with much lower computational cost (up to three orders of magnitude reduced computation time) for the property of interest. Both the smallest RVE size and the minimum number of realizations for a microstructure with higher volume fraction (VF) are larger compared to those of one with lower VF at the same desired precision. Similarly, a clustered structure is shown to require a larger minimum RVE size as well as a larger number of realizations at a given volume size compared to the well-dispersed microstructures.

Single-Run Single-Mask Inductively-Coupled-Plasma Reactive-Ion-Etching Process for Fabricating Suspended High-Aspect-Ratio Microstructures

NASA Astrophysics Data System (ADS)

Yang, Yao-Joe; Kuo, Wen-Cheng; Fan, Kuang-Chao

2006-01-01

In this work, we present a single-run single-mask (SRM) process for fabricating suspended high-aspect-ratio structures on standard silicon wafers using an inductively coupled plasma-reactive ion etching (ICP-RIE) etcher. This process eliminates extra fabrication steps which are required for structure release after trench etching. Released microstructures with 120 μm thickness are obtained by this process. The corresponding maximum aspect ratio of the trench is 28. The SRM process is an extended version of the standard process proposed by BOSCH GmbH (BOSCH process). The first step of the SRM process is a standard BOSCH process for trench etching, then a polymer layer is deposited on trench sidewalls as a protective layer for the subsequent structure-releasing step. The structure is released by dry isotropic etching after the polymer layer on the trench floor is removed. All the steps can be integrated into a single-run ICP process. Also, only one mask is required. Therefore, the process complexity and fabrication cost can be effectively reduced. Discussions on each SRM step and considerations for avoiding undesired etching of the silicon structures during the release process are also presented.

Development and characterization of a layer by layer ultrasound assisted spray deposition process for thin polymer films

NASA Astrophysics Data System (ADS)

Balakrishnan, Anandh

An Ultrasound assisted Atomization (UA) system has been developed and investigated to synthesize ˜20microm polyurethane thin films with uniform, repeatable thickness and microstructure. The UA system comprised a 20 kHz atomizer probe mounted on 750 W/cm2 transducer, a heated glass chamber and a rotating substrate. The rationale for the work has been built through a careful Design of Experiments (DoE) that sought to answer questions regarding the process-microstructure relationships from both the spray and material points of view. The independent variables chosen were the polymer solution weight percentage (0.2%, 2%, and 4%), power amplitude (energy) percentage supplied to the nozzle (23%, 29%, 37%, and 46%),the temperature of deposition (45°C, 80°C) and flow rate (50microL/min, 150microL/min). The research questions focused on influence of the process parameters on the microstructure and properties of the film. One of the problems involved fixing the trajectory of the spray and also making use of the droplet surfaces created by the spray. To achieve this, a simple air-draft attachment was devised and the influence of the same was evaluated through process and film characterization experiments. A mechanism for the draft has been schematically provided. The use of such a draft to fabricate thin polymer films via ultrasound atomization has not been achieved before and represents a 'first step' in advancing this ultrasound technology. The primary findings of the work were that the film microstructure and properties were heavily influenced by the flow rate, energy of atomization, and test temperature. In addition, the droplet diameters seemed to be readily amenable to change for the 0.2 and 2% solutions and the use of the air-draft made the process feasible, repeatable and accurate. For the 4% solutions, viscosity seemed to stabilize the liquid solution film at the tip requiring larger energies of atomization. In all, relative to the 0.2% films the fracture strengths, strains and toughness values had improved vastly for 4% and 2%. Calorimetric, Small Angle X-ray scattering and Atomic Force Microscopy (AFM) measurements showed a largely phase mixed hard segment-soft segment morphology. Calorimetry showed that the 0.2% specimens showed higher melting points (between 110--130°C) indicative of greater hard domain ordering in these samples. This is not evident in the 2% and 4% samples. This trend is supported by the Small Angle X-ray scattering and AFM data. The X-ray data show larger domain sizes and greater invariants for the 0.2% samples relative to the 2% and 4% samples. The AFM phase image measurements provided hard domain widths in the same range as the X-ray measurements (10--11 nm). All of the topographical trends from AFM showed that surface morphology was affected by i) increasing atomization energies from 29%--46% of energy (decreased surface roughness from 3 nm to 2 nm for 2% films and 1 nm to 0.5 nm for 4% films); ii) increasing film fabrication temperature from 45°C--80°C (increased roughness from 3nm to 4--5nm in local spots for 2% films and from 0.5nm to 0.6 nm for 4% films), iii) decreasing flow rate of the pump from 150microL/min to 50microL/min (comparable roughness for the case of the 2% films from 3nm to 2nm). These could explain the trends in mechanical responses as a f( energy of atomization and temperature). In order to examine sample crystallinity, we performed Wide Angle X-ray Scattering which showed a fully amorphous polymer structure. The lack of any reflections indicated that the melting points observed from calorimetry were not due to long range order in the material but due to pseudo crystalline behavior. This behavior could be ascribed to the formation of urethane-urethane ordering with hydrogen bonds between them. In general, ultrasonic energy of the capillary wave causes phase mixing and the extent of phase mixing was dependent on the weight percentage of polymer solution and the type of solvent. It was highest for the 4% samples and lowest for the 0.2% samples.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plotkowski, A.; Rios, O.; Sridharan, N.

Our present research in metal additive manufacturing (AM) focuses on designing processing parameters around existing alloys designed for traditional manufacturing. However, to maximize the benefits of AM, alloys should be designed to specifically take advantage of the unique thermal conditions of these processes. Furthermore, our study focuses on the development of a design methodology for alloys in AM, using a newly developed Al-Ce alloy as an initial case study. To evaluate the candidacy of this system for fusion based additive manufacturing, single-line laser melts were made on cast Al-12Ce plates using three different beam velocities (100, 200, and 300 mm/min).more » The microstructure was evaluated in the as-melted and heat treated conditions (24 hrs at 300°C). An extremely fine microstructure was observed within the weld pools, evolving from eutectic at the outer solid-liquid boundaries to a primary Al FCC dendritic/cellular structure nearer the melt-pool centerline. We rationalized the observed microstructures through the construction of a microstructure selection map for the Al-Ce binary system, which will be used to enable future alloy design. Interestingly, the heat treated samples exhibited no microstructural coarsening.« less

Transient rheology of stimuli responsive hydrogels: Integrating microrheology and microfluidics

NASA Astrophysics Data System (ADS)

Sato, Jun

Stimuli-responsive hydrogels have diverse potential applications in the field of drug delivery, tissue engineering, agriculture, cosmetics, gene therapy, and as sensors and actuators due to their unique responsiveness to external signals, such as pH, temperature, and ionic strength. Understanding the responsiveness of hydrogel structure and rheology to these stimuli is essential for designing materials with desirable performance. However, no instrumentation and well-defined methodology are available to characterize the structural and rheological responses to rapid solvent changes. In this thesis, a new microrheology set-up is described, which allows us to quantitatively measure the transient rheological properties and microstructure of a variety of solvent-responsive complex fluids. The device was constructed by integrating particle tracking microrheology and microfluidics and offers unique experimental capabilities for performing solvent-reponse measurements on soft fragile materials without applying external shear forces. Transient analysis methods to quantitatively obtain rheological properties were also constructed, and guidelines for the trade-off between statistical validity and temporal resolution were developed to accurately capture physical transitions. Employing the new device and methodology, we successfully quantified the transient rheological and microstructural responses during gel formation and break-up, and viscosity changes of solvent-responsive complex fluids. The analysis method was expanded for heterogeneous samples, incorporating methods to quantify the microrheology of samples with broad distributions of individual particle dynamics. Transient microrheology measurements of fragile, heterogeneous, self-assembled block copolypeptide hydrogels revealed that solvent exchange via convective mixing and dialysis can lead to significantly different gel properties and that commonly applied sample preparation protocols for the characterization of soft biomaterials could lead to erroneous conclusions about microstructural dynamics. Systematic investigations by varying key parameters, like molecular structure, gel concentration, salt concentration, and tracer particle size for microrheology, revealed that subtle variations in molecular architecture can cause major changes in response dynamics. Moreover, the results showed that the method can be applied for studying gel formation and breakup kinetics. The research in this thesis facilitates the design of solvent-responsive soft materials with appropriate microstructural dynamics for in vivo applications like tissue engineering and drug delivery, and can also be applied to study the effect of solvents on self-assembly mechanisms in other responsive soft materials, such as polymer solutions and colloidal dispersions.

Understanding the Impact of Water on the Miscibility and Microstructure of Amorphous Solid Dispersions: An AFM-LCR and TEM-EDX Study.

PubMed

Li, Na; Gilpin, Christopher J; Taylor, Lynne S

2017-05-01

Miscibility is critical for amorphous solid dispersions (ASDs). Phase-separated ASDs are more prone to crystallization, and thus can lose their solubility advantage leading to product failure. Additionally, dissolution performance can be diminished as a result of phase separation in the ASD matrix. Water is known to induce phase separation during storage for some ASDs. However, the impact of water introduced during preparation has not been as thoroughly investigated to date. The purpose of this study was to develop a mechanistic understanding of the effect of water on the phase behavior and microstructure of ASDs. Evacetrapib and two polymers were selected as the model system. Atomic force microscopy coupled with Lorentz contact resonance, and transmission electron microscopy with energy dispersive X-ray spectroscopy were employed to evaluate the microstructure and composition of phase-separated ASDs. It was found that phase separation could be induced via two routes: solution-state phase separation during ASD formation caused by water absorption during film formation by a hydrophilic solvent, or solid-phase separation following exposure to high RH during storage. Water contents of as low as 2% in the organic solvent system used to dissolve the drug and polymer were found to result in phase separation in the resultant ASD film. These findings have profound implications on lab-scale ASD preparation and potentially also for industrial production. Additionally, these high-resolution imaging techniques combined with orthogonal analyses are powerful tools to visualize structural changes in ASDs, which in turn will enable better links to be made between ASD structure and performance.

Electronic nose for detecting multiple targets

NASA Astrophysics Data System (ADS)

Chakraborty, Anirban; Parthasarathi, Ganga; Poddar, Rakesh; Zhao, Weiqiang; Luo, Cheng

2006-05-01

The discovery of high conductivity in doped polyacetylene in 1977 (garnering the 2000 Nobel Prize in Chemistry for the three discovering scientists) has attracted considerable interest in the application of polymers as the semiconducting and conducting materials due to their promising potential to replace silicon and metals in building devices. Previous and current efforts in developing conducting polymer microsystems mainly focus on generating a device of a single function. When multiple micropatterns made of different conducting polymers are produced on the same substrate, many microsystems of multiple functions can be envisioned. For example, analogous to the mammalian olfactory system which includes over 1,000 receptor genes in detecting various odors (e.g., beer, soda etc.), a sensor consisting of multiple distinct conducting polymer sensing elements will be capable of detecting a number of analytes simultaneously. However, existing techniques present significant technical challenges of degradation, low throughput, low resolution, depth of field, and/or residual layer in producing conducting polymer microstructures. To circumvent these challenges, an intermediate-layer lithography method developed in our group is used to generate multiple micropatterns made of different, commonly used conducting polymers, Polypyrrole (PPy), Poly(3,4-ethylenedioxy)thiophene (PEDOT) and Polyaniline (PANI). The generated multiple micropatterns are further used in an "electronic nose" to detect water vapor, glucose, toluene and acetone.

Ceramic Nanocomposites from Tailor-Made Preceramic Polymers

PubMed Central

Mera, Gabriela; Gallei, Markus; Bernard, Samuel; Ionescu, Emanuel

2015-01-01

The present Review addresses current developments related to polymer-derived ceramic nanocomposites (PDC-NCs). Different classes of preceramic polymers are briefly introduced and their conversion into ceramic materials with adjustable phase compositions and microstructures is presented. Emphasis is set on discussing the intimate relationship between the chemistry and structural architecture of the precursor and the structural features and properties of the resulting ceramic nanocomposites. Various structural and functional properties of silicon-containing ceramic nanocomposites as well as different preparative strategies to achieve nano-scaled PDC-NC-based ordered structures are highlighted, based on selected ceramic nanocomposite systems. Furthermore, prospective applications of the PDC-NCs such as high-temperature stable materials for thermal protection systems, membranes for hot gas separation purposes, materials for heterogeneous catalysis, nano-confinement materials for hydrogen storage applications as well as anode materials for secondary ion batteries are introduced and discussed in detail. PMID:28347023

Organic microchemical performance of solvent resistant polycarbosilane based microreactor.

PubMed

Yoon, Tae-Ho; Jung, Sang-Hee; Kim, Dong-Pyo

2011-05-01

We report the successful fabrication of preceramic polymer allylhydridopolycarbosilane (AHPCS) derived microchannels with excellent organic solvent resistance and optical transparency via economic imprinting process, followed by UV and post thermal curing process at 160 degrees C for 3 h. The microchemical performance of the fabricated microreactors was evaluated by choosing two model micro chemical reactions under organic solvent conditions; syntheses of 2-aminothiazole in DMF and dimethylpyrazole in THF, and compared with glass-based microreactor having identical dimensions and batch system with analogy. It is clear that AHPCS derived microreactor showed excellent solvent resistance and chemical stability compare with glass derived microreactor made by high cost of photolithography and thermal bonding process. The novel preceramic polymer derived microreactors showed reliable mechanical and chemical stability and conversion yields compare with that of glass derived microreactors, which is very promising for developing an integrated microfluidics by adopting available microstructuring techniques of the polymers.

Micro-optical foundry: 3D lithography by freezing liquid instabilities at nanoscale

NASA Astrophysics Data System (ADS)

Grilli, S.; Coppola, S.; Vespini, V.; Merola, F.; Finizio, A.; Ferraro, P.

2012-06-01

The pyroelectric functionality of a Lithium Niobate (LN) substrate is used for non-contact manipulation of polymeric material. In this work we introduced a novel approach for fabricating a wide variety of soft solid-like microstructures, thus leading to a new concept in 3D lithography. A relatively easy to accomplish technique has been demonstrated for curing different transient stages of polymer fluids by rapid cross-linking of PDMS. The method is twofold innovative thanks to the electrode-less configuration and to the rapid formation of a wide variety of 3D solid-like structures by exploiting polymer instabilities. This new and unique technique is named "pyro-electrohydrodynamic (PEHD) lithography", meaning the generation of structures by using forces produced by electric fields generated by the pyroelectric effect. The fabrication of polymer wires, needles, pillars, cones, or microspheres is reported, and practical proofs of their use in photonics are presented.

Temperature sensor based on a polymer diffraction grating with silver nanoparticles

NASA Astrophysics Data System (ADS)

Nuzhdin, V. I.; Valeev, V. F.; Galyautdinov, M. F.; Osin, Yu. N.; Stepanov, A. L.

2018-01-01

The method is suggested for producing an optical temperature noncontact sensor on a polymer polymethylmethacrylate (PMMA) substrate with a diffraction optical element formed by implanting low-energy high-dose silver ions through a surface mask. Ion implantation is performed at an energy of 30 keV, a radiation dose of 5.0 × 1016 ion cm-2 and an ion beam current density of 2 μA cm-2 through a surface metal mask having the form of grid with square periodical holes (cells) of size 25 μm. In the course of implantation, silver nanoparticles are produced in periodical unmasked domains of irradiated PMMA. Operation of the temperature sensor on diffraction microstructures made of polymer with silver nanoparticles is demonstrated in the range from 20 °C to 95 °C by testing it with a probe radiation of a He - Ne laser.

Decreasing diameter fluctuation of polymer optical fiber with optimized drawing conditions

NASA Astrophysics Data System (ADS)

Çetinkaya, Onur; Wojcik, Grzegorz; Mergo, Pawel

2018-05-01

The diameter fluctuations of poly(methyl methacrylate) based polymer optical fibers, during drawing processes, have been comprehensively studied. In this study, several drawing parameters were selected for investigation; such as drawing tensions, preform diameters, preform feeding speeds, and argon flows. Varied drawing tensions were used to draw fibers, while other parameters were maintained at constant. At a later stage in the process, micro-structured polymer optical fibers were drawn under optimized drawing conditions. Fiber diameter deviations were reduced to 2.2%, when a 0.2 N drawing tension was employed during the drawing process. Higher drawing tensions led to higher diameter fluctuations. The Young’s modulus of fibers drawn with different tensions was also measured. Our results showed that fiber elasticity increased as drawing tensions decreased. The inhomogeneity of fibers was also determined by comparing the deviation of Young’s modulus.

Effect of microstructure of nano- and micro-particle filled polymer composites on their tribo-mechanical performance

NASA Astrophysics Data System (ADS)

Devaprakasam, D.; Hatton, P. V.; Möbus, G.; Inkson, B. J.

2008-08-01

In this work we have investigated the influence of nanoscale and microscale structure on the tribo-mechanical performance and failure mechanisms of two biocompatible dental polymer composites, with different reinforcing particulates, using advanced microscopy techniques. Nano- and micro structural analysis reveals the shape, size and distribution of the particles in the composites. In the microparticle filled polymer composite (microcomposite), the particles are of irregular shape with sharp edges with non-uniform distribution in the matrix. However, in the nanoparticle filled composites (nanocomposite), filler particles are spherical in shape with uniform distribution in the matrix. From nanoindentation measurements, hardness and reduced modulus of the microcomposite were found to be heterogeneous. However, the hardness and reduced modulus of the nanocomposite were found to be homogeneous. The nanocomposite shows better tribo-mechanical performance compared to that of the microcomposite.

Bonding to CAD-CAM Composites: An Interfacial Fracture Toughness Approach.

PubMed

Eldafrawy, M; Ebroin, M G; Gailly, P A; Nguyen, J-F; Sadoun, M J; Mainjot, A K

2018-01-01

The objective of this study was to evaluate the interfacial fracture toughness (IFT) of composite cement with dispersed filler (DF) versus polymer-infiltrated ceramic network (PICN) computer-aided design and computer-aided manufacturing (CAD-CAM) composite blocks after 2 different surface pretreatments using the notchless triangular prism (NTP) test. Two DFs (Cerasmart [CRT] and Lava Ultimate [LVA]), 2 PICNs (Enamic [ENA] and experimental PICN [EXP]), and e.max CAD lithium disilicate glass-ceramic (EMX, control) prism samples were bonded to their counterparts with Variolink Esthetic DC composite cement after either hydrofluoric acid etching (HF) or gritblasting (GR). Both procedures were followed by silanization. All samples ( n = 30 per group) were thermocycled (10,000 cycles) and tested for their IFT in a water bath at 36°C. Moreover, representative samples from each group were subjected to a developed interfacial area ratio (Sdr) measurement by profilometry and scanning electron microscopy (SEM) characterization. EXP-HF gave the highest IFT (1.85 ± 0.39 MPa·m 1/2 ), followed by EMX-HF and ENA-HF, while CRT-HF gave the lowest (0.15 ± 0.22 MPa·m 1/2 ). PICNs gave significantly better results with HF, and DF showed better results with GR. A 2-way analysis of variance indicated that there were significantly higher IFT and Sdr for PICNs than for DF. A positive correlation ( r² = 0.872) was found between IFT and Sdr. SEM characterization showed the specific microstructure of the surface of etched PICNs, indicating the presence of a retentive polymer-based honeycomb structure. Etching of the typical double-network microstructure of PICNs causes an important increase in the Sdr and IFT, while DF should be gritblasted. DF exhibited significantly lower Sdr and IFT values than PICNs. The present results show the important influence of the material class and surface texture, and consequently the micromechanical bond, on the adhesive interface performance of CAD-CAM composites.

Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi

2016-11-21

We examine the relationship between structure and ionic conductivity in salt-containing ternary polymer blends that exhibit various microstructured morphologies, including lamellae, a hexagonal phase, and a bicontinuous microemulsion, as well as the disordered phase. These blends consist of polystyrene (PS, M n ≈ 600 g/mol) and poly(ethylene oxide) (PEO, M n ≈ 400 g/mol) homopolymers, a nearly symmetric PS–PEO block copolymer (M n ≈ 4700 g/mol), and lithium bis(trifluoromethane)sulfonamide (LiTFSI). These pseudoternary blends exhibit phase behavior that parallels that of well-studied ternary polymer blends consisting of A and B homopolymers compatibilized by an AB diblock copolymer. The utility of thismore » framework is that all blends have nominally the same number of ethylene oxide, styrene, Li +, and TFSI– units, yet can exhibit a variety of microstructures depending on the relative ratio of the homopolymers to the block copolymer. For the systems studied, the ratio r = [Li +]/[EO] is maintained at 0.06, and the volume fraction of PS homopolymer is kept equal to that of PEO homopolymer plus salt. The total volume fraction of homopolymer is varied from 0 to 0.70. When heated through the order–disorder transition, all blends exhibit an abrupt increase in conductivity. However, analysis of small-angle X-ray scattering data indicates significant structure even in the disordered state for several blend compositions. By comparing the nature and structure of the disordered states with their corresponding ordered states, we find that this increase in conductivity through the order–disorder transition is most likely due to the elimination of grain boundaries. In either disordered or ordered states, the conductivity decreases as the total amount of homopolymer is increased, an unanticipated observation. This trend with increasing homopolymer loading is hypothesized to result from an increased density of “dead ends” in the conducting channel due to poor continuity across grain boundaries in the ordered state and the formation of concave interfaces in the disordered state. The results demonstrate that disordered, microphase-separated morphologies provide better transport properties than compositionally equivalent polycrystalline systems with long-range order, an important criterion when optimizing the design of polymer electrolytes.« less

X-ray imaging and controlled solidification of Al-Cu alloys toward microstructures by design

DOE PAGES

Clarke, Amy J.; Tourret, Damien; Imhoff, Seth D.; ...

2015-01-30

X-ray imaging, which permits the microscopic visualization of metal alloy solidification dynamics, can be coupled with controlled solidification to create microstructures by design. In this study, this x-ray image shows a process-derived composite microstructure being made from a eutectic Al-17.1 at.%Cu alloy by successive solidification and remelting steps.

3D filling simulation of micro- and nanostructures in comparison to iso- and variothermal injection moulding trials

NASA Astrophysics Data System (ADS)

Rytka, C.; Lungershausen, J.; Kristiansen, P. M.; Neyer, A.

2016-06-01

Flow simulations can cut down both costs and time for the development of injection moulded polymer parts with functional surfaces used in life science and optical applications. We simulated the polymer melt flow into 3D micro- and nanostructures with Moldflow and Comsol and compared the results to real iso- and variothermal injection moulding trials below, at and above the transition temperature of the polymer. By adjusting the heat transfer coefficient and the transition temperature in the simulation it was possible to achieve good correlation with experimental findings at different processing conditions (mould temperature, injection velocity) for two polymers, namely polymethylmethacrylate and amorphous polyamide. The macroscopic model can be scaled down in volume and number of elements to save computational time for microstructure simulation and to enable first and foremost the nanostructure simulation, as long as local boundary conditions such as flow front speed are transferred correctly. The heat transfer boundary condition used in Moldflow was further evaluated in Comsol. Results showed that the heat transfer coefficient needs to be increased compared to macroscopic moulding in order to represent interfacial polymer/mould effects correctly. The transition temperature is most important in the packing phase for variothermal injection moulding.

Responsive copolymers for enhanced petroleum recovery. Annual report

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, C.; Hester, R.

1994-08-01

A coordinated research program involving synthesis, characterization, and rheology has been undertaken to develop advanced polymer system which should be significantly more efficient than polymers presently used for mobility control and conformance. Unlike the relatively inefficient, traditional EOR polymers, these advanced polymer systems possess microstructural features responsive to temperature, electrolyte concentration, and shear conditions. Contents of this report include the following chapters. (1) First annual report responsive copolymers for enhanced oil recovery. (2) Copolymers of acrylamide and sodium 3-acrylamido-3-methylbutanoate. (3) Terpolymers of NaAMB, Am, and n-decylacrylamide. (4) Synthesis and characterization of electrolyte responsive terpolymers of acrylamide, N-(4-butyl)phenylacrylamide, and sodium acrylate,more » sodium-2-acrylamido-2-methylpropanesulphonate or sodium-3-acrylamido-3-methylbutanoate. (5) Synthesis and solution properties of associative acrylamido copolymers with pyrensulfonamide fluorescence labels. (6) Photophysical studies of the solution behavior of associative pyrenesulfonamide-labeled polyacrylamides. (7) Ampholytic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate with [2-(acrylamido)-2-methypropyl]trimethylammonium chloride. (8) Ampholytic terpolymers of acrylamide with sodium 2-acrylamido-2-methylpropanesulphoante and 2-acrylamido-2-methylpropanetrimethyl-ammonium chloride and (9) Polymer solution extensional behavior in porous media.« less

Modelling Polymer Deformation and Welding Behaviour during 3D Printing

NASA Astrophysics Data System (ADS)

McIlroy, Claire; Olmsted, Peter

2016-11-01

3D printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The most common method, fused deposition modelling, involves melting a thermoplastic, followed by layer-by-layer extrusion of the material to fabricate a three-dimensional object. The key to the ensuring strength at the weld between these layers is successful inter-diffusion. However, as the printed layer cools towards the glass transition temperature, the time available for diffusion is limited. In addition, the extrusion process significantly deforms the polymer micro-structure prior to welding and consequently affects how the polymers "re-entangle" across the weld. We have developed a simple model of the non-isothermal printing process to explore the effects that typical printing conditions and amorphous polymer rheology have on the ultimate weld structure. In particular, we incorporate both the stretch and orientation of the polymer using the Rolie-Poly constitutive equation to examine how the melt flows through the nozzle and is deposited onto the build plate. We then address how this deformation relaxes and contributes to the thickness and structure of the weld. National Institute for Standards and Technology (NIST) and Georgetown University.

Modelling Polymer Deformation during 3D Printing

NASA Astrophysics Data System (ADS)

McIlroy, Claire; Olmsted, Peter

Three-dimensional printing has the potential to transform manufacturing processes, yet improving the strength of printed parts, to equal that of traditionally-manufactured parts, remains an underlying issue. The fused deposition modelling technique involves melting a thermoplastic, followed by layer-by-layer extrusion to fabricate an object. The key to ensuring strength at the weld between layers is successful inter-diffusion. However, prior to welding, both the extrusion process and the cooling temperature profile can significantly deform the polymer micro-structure and, consequently, how well the polymers are able to ``re-entangle'' across the weld. In particular, polymer alignment in the flow can cause de-bonding of the layers and create defects. We have developed a simple model of the non-isothermal extrusion process to explore the effects that typical printing conditions and material rheology have on the conformation of a polymer melt. In particular, we incorporate both stretch and orientation using the Rolie-Poly constitutive equation to examine the melt structure as it flows through the nozzle, the subsequent alignment with the build plate and the resulting deformation due to the fixed nozzle height, which is typically less than the nozzle radius.

Pepsin diffusion in dairy gels depends on casein concentration and microstructure.

PubMed

Thévenot, J; Cauty, C; Legland, D; Dupont, D; Floury, J

2017-05-15

Fundamental knowledge of gastric digestion had only focused on acid diffusion from the gastric fluid, but no data are available for pepsin diffusion. Using fluorescence recovery after photobleaching technique, diffusion coefficients D of fluorescein isothiocyanate (FITC)-pepsin were measured in rennet gels across a range of casein concentrations allowing to form networks of protein aggregates with different structures. To investigate the microstructural parameters of native gels, electron microscopy image analysis were performed and qualitatively related to diffusion behavior of FITC-pepsin in these dairy gels. This study is the first report on quantification of pepsin diffusion in dairy product. Pepsin diffusion in rennet gels depends on casein concentration and microstructure. Models of polymer science can be used to assess D in dairy gel. Such data should be confronted with pepsin activity in acidic environment, and will be very useful as input parameters in mathematical models of food degradation in the human stomach. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of ionic conduction in PEO-PVDF based blend polymer electrolytes

NASA Astrophysics Data System (ADS)

Patla, Subir Kumar; Ray, Ruma; Asokan, K.; Karmakar, Sanat

2018-03-01

We investigate the effect of blend host polymer on solid polymer electrolyte (SPE) films doped with ammonium iodide (NH4I) salt using a variety of experimental techniques. Structural studies on the composite SPEs show that the blending of Poly(ethylene oxide) (PEO)-Poly(vinylidene fluoride) (PVDF) polymers in a suitable ratio enhances the amorphous fraction of the polymer matrix and facilitates fast ion conduction through it. We observe that the addition of a small amount of PVDF in the PEO host polymer enhances the ion - polymer interaction leading to more ion dissociation. As a result, the effective number of mobile charge carriers within the polymer matrix increases. Systematic investigation in these blend SPEs shows that the maximum conductivity (1.01 × 10-3 S/cm) is obtained for PEO - rich (80 wt. % PEO, 20 wt. % PVDF) composites at 35 wt. % NH4I concentration at room temperature. Interestingly, at higher salt concentrations (above 35 wt. %), the conductivity is found to decrease in this system. The reduction of conductivity at higher salt concentrations is the consequence of decrease in the carrier concentration due to the formation of an ion pair and ion aggregates. PVDF-rich compositions (20 wt. % PEO and 80 wt. % PVDF), on the other hand, show a very complex porous microstructure. We also observe a much lower ionic conductivity (maximum ˜ 10-6 S/cm at 15 wt. % salt) in these composite systems relative to PEO-rich composites.

Effect of gamma irradiation on high temperature hardness of low-density polyethylene

NASA Astrophysics Data System (ADS)

Chen, Pei-Yun; Yang, Fuqian; Lee, Sanboh

2015-11-01

Gamma irradiation can cause the change of microstructure and molecular structure of polymer, resulting in the change of mechanical properties of polymers. Using the hardness measurement, the effect of gamma irradiation on the high temperature hardness of low-density polyethylene (LDPE) was investigated. The gamma irradiation caused the increase in the melting point, the enthalpy of fusion, and the portion of crystallinity of LDPE. The Vickers hardness of the irradiated LDPE increases with increasing the irradiation dose, annealing temperature, and annealing time. The activation energy for the rate process controlling the reaction between defects linearly decreases with the irradiation dose. The process controlling the hardness evolution in LDPE is endothermic because LDPE is semi-crystalline.

Mesoscale Modeling of Deflagration-Induced Deconsolidation in Polymer-Bonded Explosives

NASA Astrophysics Data System (ADS)

Springer, H. Keo; Reaugh, J. E.; Glascoe, E. A.; Kercher, J. R.; Friedman, G.

2011-06-01

Initially intact polymer-bonded explosives can transition from conductive burning to more violent convective burning via rapid deconsolidation at higher pressures. The pressure-dependent infiltration of cracks and pores, i.e., damage, by product gases at the burn-front is a key step in the transition to convective burning. However, the relative influence of pre-existing damage and deflagration-induced damage on the transition to convective burning is not well understood. The objective of this study is to investigate the role of explosive constituent properties, microstructure, and deflagration velocity on deconsolidation. We performed simulations using the multi-physics hydrocode, ALE3D. HMX was used as the model energetic grain. We used a JWL form for the unreacted and reacted equation-of-state of the HMX. Simplified strength and failure models were used for the HMX and the binder. The propensity for deconsolidation increased with increasing grain volume fraction, increasing porosity, decreasing binder strength, and increasing deflagration velocity. These studies are important because they enable the development of deflagration-induced damage models, as well as the design of inherently safer explosives. This work performed under the auspices of the U.S. DOE by LLNL under Contract DE-AC52-07NA27344. This work was funded by the Joint DoD/DOE Munitions Technology Development Program.

Evaluation of the Lifetime and Thermal Conductivity of Dysprosia-Stabilized Thermal Barrier Coating Systems

NASA Astrophysics Data System (ADS)

Curry, Nicholas; Markocsan, Nicolaie; Östergren, Lars; Li, Xin-Hai; Dorfman, Mitch

2013-08-01

The aim of this study was the further development of dysprosia-stabilized zirconia coatings for gas turbine applications. The target for these coatings was a longer lifetime and higher insulating performance compared to today's industrial standard thermal barrier coating. Two morphologies of ceramic top coat were studied: one using a dual-layer system and the second using a polymer to generate porosity. Evaluations were carried out using a laser flash technique to measure thermal properties. Lifetime testing was conducted using thermo-cyclic fatigue testing. Microstructure was assessed with SEM and Image analysis was used to characterize porosity content. The results show that coatings with an engineered microstructure give performance twice that of the present reference coating.

Large-Area Direct Laser-Shock Imprinting of a 3D Biomimic Hierarchical Metal Surface for Triboelectric Nanogenerators.

PubMed

Jin, Shengyu; Wang, Yixiu; Motlag, Maithilee; Gao, Shengjie; Xu, Jin; Nian, Qiong; Wu, Wenzhuo; Cheng, Gary J

2018-03-01

Ongoing efforts in triboelectric nanogenerators (TENGs) focus on enhancing power generation, but obstacles concerning the economical and cost-effective production of TENGs continue to prevail. Micro-/nanostructure engineering of polymer surfaces has been dominantly utilized for boosting the contact triboelectrification, with deposited metal electrodes for collecting the scavenged energy. Nevertheless, this state-of-the-art approach is limited by the vague potential for producing 3D hierarchical surface structures with conformable coverage of high-quality metal. Laser-shock imprinting (LSI) is emerging as a potentially scalable approach for directly surface patterning of a wide range of metals with 3D nanoscale structures by design, benefiting from the ultrahigh-strain-rate forming process. Here, a TENG device is demonstrated with LSI-processed biomimetic hierarchically structured metal electrodes for efficient harvesting of water-drop energy in the environment. Mimicking and transferring hierarchical microstructures from natural templates, such as leaves, into these water-TENG devices is effective regarding repelling water drops from the device surface, since surface hydrophobicity from these biomicrostructures maximizes the TENG output. Among various leaves' microstructures, hierarchical microstructures from dried bamboo leaves are preferable regarding maximizing power output, which is attributed to their unique structures, containing both dense nanostructures and microscale features, compared with other types of leaves. Also, the triboelectric output is significantly improved by closely mimicking the hydrophobic nature of the leaves in the LSI-processed metal surface after functionalizing it with low-surface-energy self-assembled-monolayers. The approach opens doors to new manufacturable TENG technologies for economically feasible and ecologically friendly production of functional devices with directly patterned 3D biomimic metallic surfaces in energy, electronics, and sensor applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Materials for n-type organic electronics: synthesis and properties of fluoroarene-thiophene semiconductors

NASA Astrophysics Data System (ADS)

Facchetti, Antonio; Yoon, Myung-Han; Katz, Howard E.; Marks, Tobin J.

2003-11-01

Recent progress in the field of organic electronics is due to a fruitful combination of both innovative molecular design and promising low-cost material/device assembly. Targeting the first strategy, we present here the general synthesis of fluoroarene-containing thiophene-based semiconductors and the study of their properties with respect to the corresponding fluorine-free hole-transporting analogues. The new compounds have been characterized by elemental analysis, mass spectrometry, and 1H- and 19F NMR. The dramatic influence of fluorine substitution and molecular architecture has been investigated by solution/film optical absorption, fluorescence emission, and cyclic voltammetry. Single crystal data for all of the oligomers have been obtained and will be presented. Film microstructure and morphology of this new class of materials have been studied by XRD and SEM. Particular emphasis will be posed on the solution-processable oligomers and polymers.

Superhydrophobic Surface With Shape Memory Micro/Nanostructure and Its Application in Rewritable Chip for Droplet Storage.

PubMed

Lv, Tong; Cheng, Zhongjun; Zhang, Dongjie; Zhang, Enshuang; Zhao, Qianlong; Liu, Yuyan; Jiang, Lei

2016-09-21

Recently, superhydrophobic surfaces with tunable wettability have aroused much attention. Noticeably, almost all present smart performances rely on the variation of surface chemistry on static micro/nanostructure, to obtain a surface with dynamically tunable micro/nanostructure, especially that can memorize and keep different micro/nanostructures and related wettabilities, is still a challenge. Herein, by creating micro/nanostructured arrays on shape memory polymer, a superhydrophobic surface that has shape memory ability in changing and recovering its hierarchical structures and related wettabilities was reported. Meanwhile, the surface was successfully used in the rewritable functional chip for droplet storage by designing microstructure-dependent patterns, which breaks through current research that structure patterns cannot be reprogrammed. This article advances a superhydrophobic surface with shape memory hierarchical structure and the application in rewritable functional chip, which could start some fresh ideas for the development of smart superhydrophobic surface.

Rotational 3D printing of damage-tolerant composites with programmable mechanics.

PubMed

Raney, Jordan R; Compton, Brett G; Mueller, Jochen; Ober, Thomas J; Shea, Kristina; Lewis, Jennifer A

2018-02-06

Natural composites exhibit exceptional mechanical performance that often arises from complex fiber arrangements within continuous matrices. Inspired by these natural systems, we developed a rotational 3D printing method that enables spatially controlled orientation of short fibers in polymer matrices solely by varying the nozzle rotation speed relative to the printing speed. Using this method, we fabricated carbon fiber-epoxy composites composed of volume elements (voxels) with programmably defined fiber arrangements, including adjacent regions with orthogonally and helically oriented fibers that lead to nonuniform strain and failure as well as those with purely helical fiber orientations akin to natural composites that exhibit enhanced damage tolerance. Our approach broadens the design, microstructural complexity, and performance space for fiber-reinforced composites through site-specific optimization of their fiber orientation, strain, failure, and damage tolerance. Copyright © 2018 the Author(s). Published by PNAS.

Three-dimensional printing of freeform helical microstructures: a review.

PubMed

Farahani, R D; Chizari, K; Therriault, D

2014-09-21

Three-dimensional (3D) printing is a fabrication method that enables creation of structures from digital models. Among the different structures fabricated by 3D printing methods, helical microstructures attracted the attention of the researchers due to their potential in different fields such as MEMS, lab-on-a-chip systems, microelectronics and telecommunications. Here we review different types of 3D printing methods capable of fabricating 3D freeform helical microstructures. The techniques including two more common microfabrication methods (i.e., focused ion beam chemical vapour deposition and microstereolithography) and also five methods based on computer-controlled robotic direct deposition of ink filament (i.e., fused deposition modeling, meniscus-confined electrodeposition, conformal printing on a rotating mandrel, UV-assisted and solvent-cast 3D printings) and their advantages and disadvantages regarding their utilization for the fabrication of helical microstructures are discussed. Focused ion beam chemical vapour deposition and microstereolithography techniques enable the fabrication of very precise shapes with a resolution down to ∼100 nm. However, these techniques may have material constraints (e.g., low viscosity) and/or may need special process conditions (e.g., vacuum chamber) and expensive equipment. The five other techniques based on robotic extrusion of materials through a nozzle are relatively cost-effective, however show lower resolution and less precise features. The popular fused deposition modeling method offers a wide variety of printable materials but the helical microstructures manufactured featured a less precise geometry compared to the other printing methods discussed in this review. The UV-assisted and the solvent-cast 3D printing methods both demonstrated high performance for the printing of 3D freeform structures such as the helix shape. However, the compatible materials used in these methods were limited to UV-curable polymers and polylactic acid (PLA), respectively. Meniscus-confined electrodeposition is a flexible, low cost technique that is capable of fabricating 3D structures both in nano- and microscales including freeform helical microstructures (down to few microns) under room conditions using metals. However, the metals suitable for this technique are limited to those that can be electrochemically deposited with the use of an electrolyte solution. The highest precision on the helix geometry was achieved using the conformal printing on a rotating mandrel. This method offers the lowest shape deformation after printing but requires more tools (e.g., mandrel, motor) and the printed structure must be separated from the mandrel. Helical microstructures made of multifunctional materials (e.g., carbon nanotube nanocomposites, metallic coated polymer template) were used in different technological applications such as strain/load sensors, cell separators and micro-antennas. These innovative 3D microsystems exploiting the unique helix shape demonstrated their potential for better performance and more compact microsystems.

Thiolene and SIFEL-based Microfluidic Platforms for Liquid-Liquid Extraction

PubMed Central

Goyal, Sachit; Desai, Amit V.; Lewis, Robert W.; Ranganathan, David R.; Li, Hairong; Zeng, Dexing; Reichert, David E.; Kenis, Paul J.A.

2014-01-01

Microfluidic platforms provide several advantages for liquid-liquid extraction (LLE) processes over conventional methods, for example with respect to lower consumption of solvents and enhanced extraction efficiencies due to the inherent shorter diffusional distances. Here, we report the development of polymer-based parallel-flow microfluidic platforms for LLE. To date, parallel-flow microfluidic platforms have predominantly been made out of silicon or glass due to their compatibility with most organic solvents used for LLE. Fabrication of silicon and glass-based LLE platforms typically requires extensive use of photolithography, plasma or laser-based etching, high temperature (anodic) bonding, and/or wet etching with KOH or HF solutions. In contrast, polymeric microfluidic platforms can be fabricated using less involved processes, typically photolithography in combination with replica molding, hot embossing, and/or bonding at much lower temperatures. Here we report the fabrication and testing of microfluidic LLE platforms comprised of thiolene or a perfluoropolyether-based material, SIFEL, where the choice of materials was mainly guided by the need for solvent compatibility and fabrication amenability. Suitable designs for polymer-based LLE platforms that maximize extraction efficiencies within the constraints of the fabrication methods and feasible operational conditions were obtained using analytical modeling. To optimize the performance of the polymer-based LLE platforms, we systematically studied the effect of surface functionalization and of microstructures on the stability of the liquid-liquid interface and on the ability to separate the phases. As demonstrative examples, we report (i) a thiolene-based platform to determine the lipophilicity of caffeine, and (ii) a SIFEL-based platform to extract radioactive copper from an acidic aqueous solution. PMID:25246730

Laser-assisted patterning of double-sided adhesive tapes for optofluidic chip integration

NASA Astrophysics Data System (ADS)

Zamora, Vanessa; Janeczka, Christian; Arndt-Staufenbiel, Norbert; Havlik, George; Queisser, Marco; Schröder, Henning

2018-02-01

Portable high-sensitivity biosensors exhibit a growing demand in healthcare, food industry and environmental monitoring sectors. Optical biosensors based on photonic integration platforms are attractive candidates due to their high sensitivity, compactness and multiplexing capabilities. However, they need a low-cost and reliable integration with the microfluidic system. Laser-micropatterned double-sided biocompatible adhesive tapes are promising bonding layers for hybrid integration of an optofluidic biochip. As a part of the EU-PHOCNOSIS project, double-sided adhesive tapes have been proposed to integrate the polymer microfluidic system with the optical integrated waveguide sensor chip. Here the adhesive tape should be patterned in a micrometer scale in order to create an interaction between the sample that flows through the polymer microchannel and the photonic sensing microstructure. Three laser-assisted structuring methods are investigated to transfer microchannel patterns to the adhesive tape. The test structure design consists of a single channel with 400 μm wide, 30 mm length and two circular receivers with 3 mm radius. The best structuring results are found by using the picosecond UV laser where smooth and straight channel cross-sections are obtained. Such patterned tapes are used to bond blank polymer substrates to blank silicon substrates. As a proof of concept, the hybrid integration is tested using colored DI-water. Structuring tests related to the reduction of channel widths are also considered in this work. The use of this technique enables a simple and rapid manufacturing of narrow channels (50-60 μm in width) in adhesive tapes, achieving a cheap and stable integration of the optofluidic biochip.

Responsive copolymers for enhanced petroleum recovery. Quarterly technical progress report, December 21, 1994--March 22, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, C.; Hester, R.

The purpose of this study is to extend the concept of micellar polymerization to more complex systems, and to explore the responsive nature of hydrophobically modified polyelectrolytes by tailoring the microstructure. The synthesis of hydrophobically modified acrylamide/acrylic acid copolymer is described. These types of polymers are of interest as thickening agents utilized in enhanced oil recovery.

Microstructure and Dynamic Failure Properties of Freeze-Cast Materials for Thermobaric Warhead Cases

DTIC Science & Technology

2012-12-01

Function LLNL Lawrence Livermore National Laboratory PDF Probability Density Function PMMA Poly(Methyl Methacrylate) RM Reactive Materials SEM...FREEZE CAST MATERIALS Freeze casting technology combines compounds such as aluminum oxide and poly(methyl methacrylate) ( PMMA ) to develop a...Subsequently, the porous structure can be infiltrated with a variety of materials, such as a standard polymer like PMMA . This hybrid material is believed

Balancing the Rates of New Bone Formation and Polymer Degradation Enhances Healing of Weight-Bearing Allograft/Polyurethane Composites in Rabbit Femoral Defects

DTIC Science & Technology

2014-10-03

frac tures? J Orthop Res 29, 33, 2011. Epub 2010/07/08. 2. Russell, T.A., and Leighton , R.K. Comparison of autogenous bone graft and endothermic...Boyd, S.K., Christiansen , B.A., Guldberg, R.E., Jepsen, K.J., and Muller, R. Guidelines for assessment of bone microstructure in rodents using micro

Multi-length Scale Material Model Development for Armorgrade Composites

DTIC Science & Technology

2014-05-02

various microstructural features and processes , at different length- scales, to the macroscopic-level ballistic-penetration resistance of PPTA-based...fabric or PPTA-fiber-reinforced polymer-matrix composites. Specifically, the role of various material-synthesis-/fiber- processing -induced defects, as...well as defects induced during the weaving process , was investigated. The results obtained clearly revealed that 1. REPORT DATE (DD-MM-YYYY) 4. TITLE

Machine learning strategy for accelerated design of polymer dielectrics

DOE PAGES

Mannodi-Kanakkithodi, Arun; Pilania, Ghanshyam; Huan, Tran Doan; ...

2016-02-15

The ability to efficiently design new and advanced dielectric polymers is hampered by the lack of sufficient, reliable data on wide polymer chemical spaces, and the difficulty of generating such data given time and computational/experimental constraints. Here, we address the issue of accelerating polymer dielectrics design by extracting learning models from data generated by accurate state-of-the-art first principles computations for polymers occupying an important part of the chemical subspace. The polymers are ‘fingerprinted’ as simple, easily attainable numerical representations, which are mapped to the properties of interest using a machine learning algorithm to develop an on-demand property prediction model. Further,more » a genetic algorithm is utilised to optimise polymer constituent blocks in an evolutionary manner, thus directly leading to the design of polymers with given target properties. Furthermore, while this philosophy of learning to make instant predictions and design is demonstrated here for the example of polymer dielectrics, it is equally applicable to other classes of materials as well.« less

The role of energetic ions from plasma in the creation of nanostructured materials and stable polymer surface treatments

NASA Astrophysics Data System (ADS)

Bilek, M. M. M.; Newton-McGee, K.; McKenzie, D. R.; McCulloch, D. G.

2006-01-01

Plasma processes for the synthesis of new materials as thin films have enabled the production of a wide variety of new materials. These include meta-stable phases, which are not readily found in nature, and more recently, materials with structure on the nanoscale. Study of plasma synthesis processes at the fundamental level has revealed that ion energy, depositing flux and growth surface temperature are the critical parameters affecting the microstructure and the properties of the thin film materials formed. In this paper, we focus on the role of ion flux and impact energy in the creation of thin films with nanoscale structure in the form of multilayers. We describe three synthesis strategies, based on the extraction of ions from plasma sources and involving modulation of ion flux and ion energy. The microstructure, intrinsic stress and physical properties of the multilayered samples synthesized are studied and related back to the conditions at the growth surface during deposition. When energetic ions of a non-condensing species are used, it is possible to place active groups on the surfaces of materials such as polymers. These active groups can then be used as bonding sites in subsequent chemical attachment of proteins or other macromolecules. If the energy of the non-condensing ions is increased to a few keV then modified layers buried under the surface can be produced. Here we describe a method by which the aging effect, which is often observed in plasma surface modifications on polymers, can be reduced and even eliminated using high energy ion bombardment.

Southern Regional Center for Lightweight Innovative Design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Paul T.

The Southern Regional Center for Lightweight Innovative Design (SRCLID) has developed an experimentally validated cradle-to-grave modeling and simulation effort to optimize automotive components in order to decrease weight and cost, yet increase performance and safety in crash scenarios. In summary, the three major objectives of this project are accomplished: To develop experimentally validated cradle-to-grave modeling and simulation tools to optimize automotive and truck components for lightweighting materials (aluminum, steel, and Mg alloys and polymer-based composites) with consideration of uncertainty to decrease weight and cost, yet increase the performance and safety in impact scenarios; To develop multiscale computational models that quantifymore » microstructure-property relations by evaluating various length scales, from the atomic through component levels, for each step of the manufacturing process for vehicles; and To develop an integrated K-12 educational program to educate students on lightweighting designs and impact scenarios. In this final report, we divided the content into two parts: the first part contains the development of building blocks for the project, including materials and process models, process-structure-property (PSP) relationship, and experimental validation capabilities; the second part presents the demonstration task for Mg front-end work associated with USAMP projects.« less

Visible light curing of Epon SU-8 based superparamagnetic polymer composites with random and ordered particle configurations.

PubMed

Peters, Christian; Ergeneman, Olgaç; Sotiriou, Georgios A; Choi, Hongsoo; Nelson, Bradley J; Hierold, Christofer

2015-01-14

The performance of superparamagnetic polymer composite microdevices is highly dependent on the magnetic particle content. While high loading levels are desired for many applications, the UV absorption of these nanoparticles limits the overall thickness of the fabricated microstructures and subsequently their capability of magnetic interaction. The combination of a visible-light-sensitive photoinitiator and particle self-organization is proposed to extend the exposure depth limitation in Epon SU-8 based superparamagnetic polymer composites. While superparamagnetic iron oxide particles strongly absorb i-line radiation required to cross-link the Epon SU-8 polymer matrix, we propose the utilization of H-Nu 470 photoinitiator to expand the photosensitivity of the composite toward the visible spectrum, where the dispersed nanoparticles are more transparent. The novel photoinitiator preserves the composite's superparamagnetic properties as well as a homogeneous particle distribution. As a result, particle load or resist thickness can be more than doubled while maintaining exposure time. The self-organization of ordered magnetic structures allows for an additional increase in exposure depth of up to 40%, resulting in a 2.5-fold saturation magnetization.

Nuclear Instruments and Methods in Physics Research. Section B; Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Pater, Ruth H.; Eftekhari, Abe

1998-01-01

Thermoset and thermoplastic polyimides have complementary physical/mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. It is expected that a combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPNs) of thermoset LaRC(Trademark)-RP46 and thermoplastic LARC(Trademark)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0: 100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical/mechanical properties. As expected, positronium atoms are not formed in these samples. The second life time component has been used to infer the positron trap dimensions. The "free volume" goes through a minimum at about 50:50 ratio, suggesting that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples have been discussed in this paper.

Automated Dispersion and Orientation Analysis for Carbon Nanotube Reinforced Polymer Composites

PubMed Central

Gao, Yi; Li, Zhuo; Lin, Ziyin; Zhu, Liangjia; Tannenbaum, Allen; Bouix, Sylvain; Wong, C.P.

2012-01-01

The properties of carbon nanotube (CNT)/polymer composites are strongly dependent on the dispersion and orientation of CNTs in the host matrix. Quantification of the dispersion and orientation of CNTs by microstructure observation and image analysis has been demonstrated as a useful way to understand the structure-property relationship of CNT/polymer composites. However, due to the various morphologies and large amount of CNTs in one image, automatic and accurate identification of CNTs has become the bottleneck for dispersion/orientation analysis. To solve this problem, shape identification is performed for each pixel in the filler identification step, so that individual CNT can be exacted from images automatically. The improved filler identification enables more accurate analysis of CNT dispersion and orientation. The obtained dispersion index and orientation index of both synthetic and real images from model compounds correspond well with the observations. Moreover, these indices help to explain the electrical properties of CNT/Silicone composite, which is used as a model compound. This method can also be extended to other polymer composites with high aspect ratio fillers. PMID:23060008

Microstructure and conductivity of in-situ polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) crystals

NASA Astrophysics Data System (ADS)

Liu, Jinglin; Ouyang, Liangqi; Wu, Jinghang; Kuo, Chin-Chen; Wei, Bin; Martin, David

2013-03-01

Conjugated polymers are widely used in organic solar cells, biomedical devices, and chemical sensors. Both chemical and electrochemical methods have been developed for preparing conducting polymers, but the extent of crystalline order is usually modest. Here we synthesized highly-ordered brominated (3,4-ethylenedioxythiophene) (EDOT-Br) monomer crystals via electrochemical methods. The kinetics of the synthesis was studied with a Quartz Crystal Microbalance (QCM) and Cyclic Voltammetry (CV). The chemical structure of the EDOT-Br monomer has been confirmed by Nuclear Magnetic Resonance (NMR), Ultraviolet-Visible Spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), and Mass Spectrometry (MS). The EDOT-Br monomer crystals can be in-situ polymerized into highly ordered PEDOT conjugated polymer crystals by annealing at temperatures below the EDOT-Br melting point. The crystalline structure was studied by optical microscopy, electron microscopy and X-Ray analysis. The conductivity and electrochemical properties of both the EDOT-Br monomer and corresponding PEDOT polymer crystals were examined with electrochemical impedance spectroscopy (EIS) and CV. This work was supported by NSF, DMR- 1103027.

Investigation of Polymer Liquid Crystals

NASA Technical Reports Server (NTRS)

Han, Kwang S.

1996-01-01

The positron annihilation lifetime spectroscopy (PALS) using a low energy flux generator may provide a reasonably accurate technique for measuring molecular weights of linear polymers and characterization of thin polyimide films in terms of their dielectric constants and hydrophobity etc. Among the tested samples are glassy poly arylene Ether Ketone films, epoxy and other polyimide films. One of the proposed techniques relates the free volume cell size (V(sub f)) with sample molecular weight (M) in a manner remarkably similar to that obtained by Mark Houwink (M-H) between the inherent viscosity (eta) and molecular wieght of polymer solution. The PALS has also demonstrated that free-volume cell size in thermoset is a versatile, useful parameter that relates directly to the polymer segmental molecular weight, the cross-link density, and the coefficient of thermal expansion. Thus, a determination of free volume cell size provides a viable basis for complete microstructural characterization of thermoset polyimides and also gives direct information about the cross-link density and coefficient of expansion of the test samples. Seven areas of the research conducted are reported here.

Improved electron transport properties of n-type naphthalenediimide polymers through refined molecular ordering and orientation induced by processing solvents.

PubMed

An, Yujin; Long, Dang Xuan; Kim, Yiho; Noh, Yong-Young; Yang, Changduk

2016-05-14

To determine the role played by the choice of processing solvents in governing the photophysics, microstructure, and charge carrier transport in naphthalenediimide (NDI)-based polymers, we have prepared two new NDI-bithiophene (T2)- and NDI-thienothiophene (TTh)-containing polymers with hybrid siloxane pentyl chains (SiC5) (P(NDI2SiC5-T2) and P(NDI2SiC5-TTh)). Among the various processing solvents studied here, the films prepared using chloroform exhibited far better electron mobilities (0.16 ± 0.1-0.21 ± 0.05 cm(2) V(-1) s(-1)) than the corresponding samples prepared from different solvents, exceeding one order of magnitude higher, indicating the significant influence of the processing solvent on the charge transport. Upon thin-film analysis using atomic force microscopy and grazing incidence X-ray diffraction, we discovered that molecular ordering and orientation are affected by the choice of the processing solvent, which is responsible for the change in the transport characteristics of this class of polymers.

Evaluation of an Al-Ce alloy for laser additive manufacturing

DOE PAGES

Plotkowski, A.; Rios, O.; Sridharan, N.; ...

2016-12-27

Our present research in metal additive manufacturing (AM) focuses on designing processing parameters around existing alloys designed for traditional manufacturing. However, to maximize the benefits of AM, alloys should be designed to specifically take advantage of the unique thermal conditions of these processes. Furthermore, our study focuses on the development of a design methodology for alloys in AM, using a newly developed Al-Ce alloy as an initial case study. To evaluate the candidacy of this system for fusion based additive manufacturing, single-line laser melts were made on cast Al-12Ce plates using three different beam velocities (100, 200, and 300 mm/min).more » The microstructure was evaluated in the as-melted and heat treated conditions (24 hrs at 300°C). An extremely fine microstructure was observed within the weld pools, evolving from eutectic at the outer solid-liquid boundaries to a primary Al FCC dendritic/cellular structure nearer the melt-pool centerline. We rationalized the observed microstructures through the construction of a microstructure selection map for the Al-Ce binary system, which will be used to enable future alloy design. Interestingly, the heat treated samples exhibited no microstructural coarsening.« less

Interfacial crowding of nanoplatelets in co-continuous polymer blends: assembly, elasticity and structure of the interfacial nanoparticle network.

PubMed

Altobelli, R; Salzano de Luna, M; Filippone, G

2017-09-27

The sequence of events which leads to the interfacial crowding of plate-like nanoparticles in co-continuous polymer blends is investigated through a combination of morphological and rheological analyses. Very low amounts (∼0.2 vol%) of organo-modified clay are sufficient to suppress phase coarsening in a co-continuous polystyrene/poly(methyl methacrylate) blend, while lower particle loading allows for a tuning of the characteristic size of the polymer phases at the μm-scale. In any case, an interfacial network of nanoparticles eventually forms, which is driven by the preferred polymer-polymer interface. The elastic features and stress-bearing ability of this peculiar nanoparticle assembly are studied in detail by means of a descriptive two-phase viscoelastic model, which allows isolation of the contribution of the filler network. The role of the co-continuous matrix in driving the space arrangement of the nanoparticles is emphasized by means of comparative analysis with systems based on the same polymers and nanoparticles, but in which the matrix is either a pure polymer or a blend with drop-in-matrix morphology. The relaxation dynamics of the interfacial network was found not to depend on the matrix microstructure, which instead substantially affects the assembly of the nanoplatelets. When the host medium is co-continuous, the particles align along the preferred polymer-polymer interface, percolating at a very low amount (∼0.17 vol%) and prevalently interacting edge-to-edge. The stress bearing ability of such a network is much higher than that in the case of matrix based on a homogeneous polymer or a drop-in-matrix blend, but its elasticity shows low sensitivity to the filler content.

Macro and micro analysis of small molecule diffusion in amorphous polymers

NASA Astrophysics Data System (ADS)

Putta, Santosh Krishna

In this study, both macroscopic and microscopic numerical techniques have been explored, to model and understand the diffusion behavior of small molecules in amorphous polymers, which very often do not follow the classical Fickian law. It was attempted to understand the influence of various aspects of the molecular structure of a polymer on its macroscopic diffusion behavior. At the macroscopic level, a hybrid finite-element/finite-difference model is developed to implement the coupled diffusion and deformation constitutive equations. A viscoelasticity theory, combined with time-freevolume superposition is used to model the deformation processes. A freevolume-based model is used to model the diffusion processes. The freevolume in the polymer is used as a coupling factor between the deformation and the diffusion processes. The model is shown to qualitatively describe some of the typical non-Fickian diffusion behavior in polymers. However, it does not directly involve the microstructure of a polymer. Further, some of the input parameters to the model are difficult to obtain experimentally. A numerical microscopic approach is therefore adopted to study the molecular structure of polymers. A molecular mechanics and dynamics technique combined with a modified Rotational Isomeric State (RIS) approach, is followed to generate the molecular structure for two types of polycarbonates, and, two types of polyacrylates, starting only with their chemical structures. A new efficient 3-D algorithm for Delaunay Tessellation is developed, and, then applied to discretize the molecular structure into Delaunay Tetrahedra. By using the dicretized molecular structure, size, shape, and, connectivity of free-spaces for small molecule diffusion in the above mentioned polymers, are then studied in relation to their diffusion properties. The influence of polymer and side chain flexibility, and diffusant-diffusant and diffusant-polymer molecular interactions, is also discussed with respect to the diffusion properties.

Multiscale structure, interfacial cohesion, adsorbed layers, miscibility and properties in dense polymer-particle mixtures

NASA Astrophysics Data System (ADS)

Schweizer, Ken

2012-02-01

A major goal in polymer nanocomposite research is to understand and predict how the chemical and physical nature of individual polymers and nanoparticles, and thermodynamic state (temperature, composition, solvent dilution, filler loading), determine bulk assembly, miscibility and properties. Microscopic PRISM theory provides a route to this goal for equilibrium disordered mixtures. A major prediction is that by manipulating the net polymer-particle interfacial attraction, miscibility is realizable via the formation of thin thermodynamically stable adsorbed layers, which, however, are destroyed by entropic depletion and bridging attraction effects if interface cohesion is too weak or strong, respectively. This and related issues are quantitatively explored for miscible mixtures of hydrocarbon polymers, silica nanospheres, and solvent using x-ray scattering, neutron scattering and rheology. Under melt conditions, quantitative agreement between theory and silica scattering experiments is achieved under both steric stabilization and weak depletion conditions. Using contrast matching neutron scattering to characterize the collective structure factors of polymers, particles and their interface, the existence and size of adsorbed polymer layers, and their consequences on microstructure, is determined. Failure of the incompressible RPA, accuracy of PRISM theory, the nm thickness of adsorbed layers, and qualitative sensitivity of the bulk modulus to interfacial cohesion and particle size are demonstrated for concentrated PEO-silica-ethanol nanocomposites. Temperature-dependent complexity is discovered when water is the solvent, and nonequilibrium effects emerge for adsorbing entangled polymers that strongly impact structure. By varying polymer chemistry, the effect of polymer-particle attraction on the intrinsic viscosity is explored with striking non-classical effects observed. This work was performed in collaboration with S.Y.Kim, L.M.Hall, C.Zukoski and B.Anderson.

A small-angle x-ray scattering system with a vertical layout.

PubMed

Wang, Zhen; Chen, Xiaowei; Meng, Lingpu; Cui, Kunpeng; Wu, Lihui; Li, Liangbin

2014-12-01

A small-angle x-ray scattering (SAXS) system with a vertical layout (V-SAXS) has been designed and constructed for in situ detection on nanostructures, which is well suitable for in situ study on self-assembly of nanoparticles at liquid interface and polymer processing. A steel-tower frame on a reinforced basement is built as the supporting skeleton for scattering beam path and detector platform, ensuring the system a high working stability and a high operating accuracy. A micro-focus x-ray source combining parabolic three-dimensional multi-layer mirror and scatteringless collimation system provides a highly parallel beam, which allows us to detect the very small angle range. With a sample-to-detector distance of 7 m, the largest measurable length scale is 420 nm in real space. With a large sample zone, it is possible to install different experimental setups such as film stretching machine, which makes the system perfect to follow the microstructures evolution of materials during processing. The capability of the V-SAXS on in situ study is tested with a drying experiment of a free latex droplet, which confirms our initial design.

Effects of build parameters on linear wear loss in plastic part produced by fused deposition modeling

NASA Astrophysics Data System (ADS)

Mohamed, Omar Ahmed; Masood, Syed Hasan; Bhowmik, Jahar Lal

2017-07-01

Fused Deposition Modeling (FDM) is one of the prominent additive manufacturing technologies for producing polymer products. FDM is a complex additive manufacturing process that can be influenced by many process conditions. The industrial demands required from the FDM process are increasing with higher level product functionality and properties. The functionality and performance of FDM manufactured parts are greatly influenced by the combination of many various FDM process parameters. Designers and researchers always pay attention to study the effects of FDM process parameters on different product functionalities and properties such as mechanical strength, surface quality, dimensional accuracy, build time and material consumption. However, very limited studies have been carried out to investigate and optimize the effect of FDM build parameters on wear performance. This study focuses on the effect of different build parameters on micro-structural and wear performance of FDM specimens using definitive screening design based quadratic model. This would reduce the cost and effort of additive manufacturing engineer to have a systematic approachto make decision among the manufacturing parameters to achieve the desired product quality.

Microstructure design of nanoporous TiO2 photoelectrodes for dye-sensitized solar cell modules.

PubMed

Hu, Linhua; Dai, Songyuan; Weng, Jian; Xiao, Shangfeng; Sui, Yifeng; Huang, Yang; Chen, Shuanghong; Kong, Fantai; Pan, Xu; Liang, Linyun; Wang, Kongjia

2007-01-18

The optimization of dye-sensitized solar cells, especially the design of nanoporous TiO2 film microstructure, is an urgent problem for high efficiency and future commercial applications. However, up to now, little attention has been focused on the design of nanoporous TiO2 microstructure for a high efficiency of dye-sensitized solar cell modules. The optimization and design of TiO2 photoelectrode microstructure are discussed in this paper. TiO2 photoelectrodes with three different layers, including layers of small pore size films, larger pore size films, and light-scattering particles on the conducting glass with the desirable thickness, were designed and investigated. Moreover, the photovoltaic properties showed that the different porosities, pore size distribution, and BET surface area of each layer have a dramatic influence on short-circuit current, open-circuit voltage, and fill factor of the modules. The optimization and design of TiO2 photoelectrode microstructure contribute a high efficiency of DSC modules. The photoelectric conversion efficiency around 6% with 15 x 20 cm2 modules under illumination of simulated AM1.5 sunlight (100 mW/cm2) and 40 x 60 cm2 panels with the same performance tested outdoor have been achieved by our group.

Effect of carbon nanofillers on the microstructure and electromechanical properties of electroactive polymers

NASA Astrophysics Data System (ADS)

Sigamani, Nirmal Shankar

Both ionic and electronic electroactive polymers (EAPs) have displayed great potential as actuators. Current ionic EAPs have limited practical application due to their slow response time and their low blocked force; furthermore, their ion transport-based mechanism necessitates the presence of an electrolyte, which complicates issues of packaging and device lifetime. On the other hand, despite the advantages of electronic EAPs such as their efficient electromechanical coupling and relatively rapid response time, there are major obstacles blocking their transition to application as well; most notably, they require high actuation voltages (threshold voltage needed to generate electroactive strain) and they have low blocked stress (the stress at which the actuator stops moving). Hence, the main objective of this study was to develop a new kind of polymer nanocomposite for actuator applications that would exhibit simultaneous improvement in both electromechanical response and strain energy density. As a first step, we investigated the impact of the 2-dimensional GO and reduced GO on the electromechanical response of PVDF, a polar polymer. The 1 wt % reduced-GO-PVDF nanocomposites showed a tremendous improvement in dielectric permittivity and electrical conductivity. The dielectric permittivity at 1 KHz increased almost eight fold, while the electrical conductivity showed an increase of four orders of magnitude in comparison to the corresponding values for the unmodified PVDF. The reduced GO-PVDF polymer films showed a bending actuation response with a DC electric field, thus demonstrating its potential as EAP. The mechanism responsible for this bending actuation response is determined to be electrostriction, because the strain (S11) exhibited a quadratic response with the applied electric field while Joule heating and Maxwell stress effects were shown to be negligible. Although coefficient of electrostriction of reduced GO-PVDF is higher than most of the existing electroactive polymers, the relatively high electrical conductivity and low breakdown limits their use for practical applications. So next step was to exploit the advantages of a conductive carbon nanostructure while controlling its network to better impact its electrical properties which could also lead to higher breakdown strength. Based on the promising impact of hybrid nanofillers on the ferroelectric polymer PVDF, a similar polymer with a relaxor ferroelectric character is considered owing to its higher inherent electroactive response and higher breakdown strength. Given that it is not broadly studied, there was a need to understand structure-property relationship of the PVDF TrFE CTFE terpolymer. Hence, the effect of processing conditions (such as annealing times and isothermal crystallization temperatures) on the microstructure and the subsequent electromechanical properties were analyzed. This structure-property analysis helped to understand the relation between the different types of crystalline phases and the degrees of crystallinity as well as to observe crystal sizes as they relate to the electric field induced strain. As a final step, the effect of the hybrid SWNT/GO on both microstructure and electromechanical properties of the terpolymer were studied. The hybrid nanofillers were chemically modified to form a covalent bond between them to improve their interaction. The morphology of the hybrid nanofillers after the chemical modification was studied for two different chemical modification routes: one using thionyl chloride, other using NHS and EDAC as catalysts. Of the two methods, the NHS and EDAC catalyst method showed a strong uniform interaction, confirmed by SEM images and FTIR results, with a shift in the peak to 1630 cm-1. Finally, the effect of hybrid SWNT and GO on the electromechanical properties were studied and, interestingly, the hybrid terpolymer nanocomposite film showed a lower electroactive strain compared to pure terpolymer at the same applied electric field. WAXS and DSC results suggest that this reduction is partly due to the change in the crystallinity and to the SWNT hindrance effect on the crystalline phase transformation which is responsible for the electroactive strain. In this dissertation, it was successfully shown that using hybrid SWNT-GO both high coefficient of electrostriction (increase by 60 %) and high breakdown strength (140 MV/m) can be achieved by exploiting the actuation capabilities of SWNT in PVDF while GO acted as insulative filler. Also, the type of the fillers in the nanocomposites route had a strong influence on the actuation mechanism of relaxor ferroelectric polymers. The microstructure-property study highlights the importance of choosing the right type of nanofillers for further advancement in the field of EAPs. (Abstract shortened by UMI.).

Role of Microstructure on the Performance of UHTCs

NASA Technical Reports Server (NTRS)

Johnson, Sylvia M.; Gasch, Matthew J.; Lawson, John W.; Gusman, Michael I.; Stackpoole, Mairead

2010-01-01

We have investigated a number of methods to control microstructure. We have routes to form: a) in situ "composites" b) Very fine microstructures. Arcjet testing and other characterization of monolithic materials. Control oxidation through microstructure and composition. Beginning to incorporate these materials as matrices for composites. Modeling effort to facilitate material design and characterization.

Synthesis and supramolecular assembly of biomimetic polymers

NASA Astrophysics Data System (ADS)

Marciel, Amanda Brittany

A grand challenge in materials chemistry is the synthesis of macromolecules and polymers with precise shapes and architectures. Polymer microstructure and architecture strongly affect the resulting functionality of advanced materials, yet understanding the static and dynamic properties of these complex macromolecules in bulk has been difficult due to their inherit polydispersity. Single molecule studies have provided a wealth of information on linear flexible and semi-flexible polymers in dilute solutions. However, few investigations have focused on industrially relevant complex topologies (e.g., star, comb, hyperbranched polymers) in industrially relevant solution conditions (e.g., semi-dilute, concentrated). Therefore, from this perspective there is a strong need to synthesize precision complex architectures for bulk studies as well as complex architectures compatible with current single molecule techniques to study static and dynamic polymer properties. In this way, we developed a hybrid synthetic strategy to produce branched polymer architectures based on chemically modified DNA. Overall, this approach enables control of backbone length and flexibility, as well as branch grafting density and chemical identity. We utilized a two-step scheme based on enzymatic incorporation of non-natural nucleotides containing bioorthogonal dibenzocyclooctyne (DBCO) functional groups along the main polymer backbone, followed by copper-free "click" chemistry to graft synthetic polymer branches or oligonucleotide branches to the DNA backbone, thereby allowing for the synthesis of a variety of polymer architectures, including three-arm stars, H-polymers, graft block copolymers, and comb polymers for materials assembly and single molecule studies. Bulk materials properties are also affected by industrial processing conditions that alter polymer morphology. Therefore, in an alternative strategy we developed a microfluidic-based approach to assemble highly aligned synthetic oligopeptides nanostructures using microscale extensional flows. This strategy enabled reproducible, reliable fabrication of aligned hierarchical constructs that do not form spontaneously in solution. In this way, fluidic-directed assembly of supramolecular structures allows for unprecedented manipulation at the nano- and mesoscale, which has the potential to provide rapid and efficient control of functional materials properties.

Multifunctional Nanostructured Conductive Polymer Gels: Synthesis, Properties, and Applications

DOE PAGES

Zhao, Fei; Shi, Ye; Pan, Lijia; ...

2017-06-26

Conductive polymers have attracted significant interest over the past few decades because they synergize the advantageous features of conventional polymeric materials and organic conductors. With rationally designed nanostructures, conductive polymers can further exhibit exceptional mechanical, electrical, and optical properties because of their confined dimensions at the nanoscale level. Among various nanostructured conductive polymers, conductive polymer gels (CPGs) with synthetically tunable hierarchical 3D network structures show great potential for a wide range of applications, such as bioelectronics, and energy storage/conversion devices owing to their structural features. CPGs retain the properties of nanosized conductive polymers during the assembly of the nanobuilding blocksmore » into a monolithic macroscopic structure while generating structure-derived features from the highly cross-linked network. In this Account, we review our recent progress on the synthesis, properties, and novel applications of dopant cross-linked CPGs. We first describe the synthetic strategies, in which molecules with multiple functional groups are adopted as cross-linkers to cross-link conductive polymer chains into a 3D molecular network. These cross-linking molecules also act as dopants to improve the electrical conductivity of the gel network. The microstructure and physical/chemical properties of CPGs can be tuned by controlling the synthetic conditions such as species of monomers and cross-linkers, reaction temperature, and solvents. By incorporating other functional polymers or particles into the CPG matrix, hybrid gels have been synthesized with tailored structures. These hybrid gel materials retain the functionalities from each component, as well as enable synergic effects to improve mechanical and electrical properties of CPGs. We then introduce the unique structure-derived properties of the CPGs. The network facilitates both electronic and ionic transport owing to the continuous pathways for electrons and hierarchical pores for ion diffusion. CPGs also provide high surface area and solvent compatibility, similar to natural gels. With these improved properties, CPGs have been explored to enable novel conceptual devices in diverse applications from smart electronics and ultrasensitive biosensors, to energy storage and conversion devices. CPGs have also been adopted for developing hybrid materials with multifunctionalities, such as stimuli responsiveness, self-healing properties, and super-repellency to liquid. With synthetically tunable physical/chemical properties, CPGs emerge as a unique material platform to develop novel multifunctional materials that have the potential to impact electronics, energy, and environmental technologies. Our hope is that this Account promotes further efforts toward synthetic control, fundamental investigation, and application exploration of CPGs.« less

Multifunctional Nanostructured Conductive Polymer Gels: Synthesis, Properties, and Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Fei; Shi, Ye; Pan, Lijia

Conductive polymers have attracted significant interest over the past few decades because they synergize the advantageous features of conventional polymeric materials and organic conductors. With rationally designed nanostructures, conductive polymers can further exhibit exceptional mechanical, electrical, and optical properties because of their confined dimensions at the nanoscale level. Among various nanostructured conductive polymers, conductive polymer gels (CPGs) with synthetically tunable hierarchical 3D network structures show great potential for a wide range of applications, such as bioelectronics, and energy storage/conversion devices owing to their structural features. CPGs retain the properties of nanosized conductive polymers during the assembly of the nanobuilding blocksmore » into a monolithic macroscopic structure while generating structure-derived features from the highly cross-linked network. In this Account, we review our recent progress on the synthesis, properties, and novel applications of dopant cross-linked CPGs. We first describe the synthetic strategies, in which molecules with multiple functional groups are adopted as cross-linkers to cross-link conductive polymer chains into a 3D molecular network. These cross-linking molecules also act as dopants to improve the electrical conductivity of the gel network. The microstructure and physical/chemical properties of CPGs can be tuned by controlling the synthetic conditions such as species of monomers and cross-linkers, reaction temperature, and solvents. By incorporating other functional polymers or particles into the CPG matrix, hybrid gels have been synthesized with tailored structures. These hybrid gel materials retain the functionalities from each component, as well as enable synergic effects to improve mechanical and electrical properties of CPGs. We then introduce the unique structure-derived properties of the CPGs. The network facilitates both electronic and ionic transport owing to the continuous pathways for electrons and hierarchical pores for ion diffusion. CPGs also provide high surface area and solvent compatibility, similar to natural gels. With these improved properties, CPGs have been explored to enable novel conceptual devices in diverse applications from smart electronics and ultrasensitive biosensors, to energy storage and conversion devices. CPGs have also been adopted for developing hybrid materials with multifunctionalities, such as stimuli responsiveness, self-healing properties, and super-repellency to liquid. With synthetically tunable physical/chemical properties, CPGs emerge as a unique material platform to develop novel multifunctional materials that have the potential to impact electronics, energy, and environmental technologies. Our hope is that this Account promotes further efforts toward synthetic control, fundamental investigation, and application exploration of CPGs.« less

Multifunctional Nanostructured Conductive Polymer Gels: Synthesis, Properties, and Applications.

PubMed

Zhao, Fei; Shi, Ye; Pan, Lijia; Yu, Guihua

2017-07-18

Conductive polymers have attracted significant interest over the past few decades because they synergize the advantageous features of conventional polymeric materials and organic conductors. With rationally designed nanostructures, conductive polymers can further exhibit exceptional mechanical, electrical, and optical properties because of their confined dimensions at the nanoscale level. Among various nanostructured conductive polymers, conductive polymer gels (CPGs) with synthetically tunable hierarchical 3D network structures show great potential for a wide range of applications, such as bioelectronics, and energy storage/conversion devices owing to their structural features. CPGs retain the properties of nanosized conductive polymers during the assembly of the nanobuilding blocks into a monolithic macroscopic structure while generating structure-derived features from the highly cross-linked network. In this Account, we review our recent progress on the synthesis, properties, and novel applications of dopant cross-linked CPGs. We first describe the synthetic strategies, in which molecules with multiple functional groups are adopted as cross-linkers to cross-link conductive polymer chains into a 3D molecular network. These cross-linking molecules also act as dopants to improve the electrical conductivity of the gel network. The microstructure and physical/chemical properties of CPGs can be tuned by controlling the synthetic conditions such as species of monomers and cross-linkers, reaction temperature, and solvents. By incorporating other functional polymers or particles into the CPG matrix, hybrid gels have been synthesized with tailored structures. These hybrid gel materials retain the functionalities from each component, as well as enable synergic effects to improve mechanical and electrical properties of CPGs. We then introduce the unique structure-derived properties of the CPGs. The network facilitates both electronic and ionic transport owing to the continuous pathways for electrons and hierarchical pores for ion diffusion. CPGs also provide high surface area and solvent compatibility, similar to natural gels. With these improved properties, CPGs have been explored to enable novel conceptual devices in diverse applications from smart electronics and ultrasensitive biosensors, to energy storage and conversion devices. CPGs have also been adopted for developing hybrid materials with multifunctionalities, such as stimuli responsiveness, self-healing properties, and super-repellency to liquid. With synthetically tunable physical/chemical properties, CPGs emerge as a unique material platform to develop novel multifunctional materials that have the potential to impact electronics, energy, and environmental technologies. We hope that this Account promotes further efforts toward synthetic control, fundamental investigation, and application exploration of CPGs.

Experimental studies on a novel roll-to-roll powder hot embossing for large-area fabrication of micropyramid arrays on polymers

NASA Astrophysics Data System (ADS)

Yi, Peiyun; Deng, Yujun; Shu, Yunyi; Peng, Linfa

2018-08-01

Roll-to-roll (R2R) hot embossing is regarded as a cost-effective replication technology to fabricate microstructures on polymer films. However, the characteristics of continuous and fast forming for the R2R hot embossing process limits material flow during the filling stage and results in significant springback during the demolding stage. To resolve this issue, this study proposed a novel R2R powder hot embossing process, which combines the merits of the continuous fabrication of R2R hot embossing and near-net-shape forming of powder sintering and also decreases the whole cycle of the fabrication from films to microstructures. First, the relation between the molten layer thickness and processing parameters was discussed and an analytical model was established to predict the feed of the polymeric powder during R2R powder hot embossing. Then, with the use of a micro-pyramid array mold, the impact of the process parameters including mold temperature, feeding speed and applied force on the geometrical dimension of the patterned microstructures was discussed. Last, based on the response surface analysis, a process window, in terms of the mold temperature of 132 °C –145 °C, feeding speed of 0.1–1.4 m min‑1 and applied force of 15–50 kgf was determined for the continuous fabrication of completely-filled micropyramid arrays with the R2R powder hot embossing process. This research demonstrated the feasibility and superiority of the proposed R2R powder hot embossing process in continuously fabricating micropatterned structures on polymeric films.

Impact of solvents and supercritical CO2 drying on the morphology and structure of polymer-based biofilms

NASA Astrophysics Data System (ADS)

Causa, Andrea; Salerno, Aurelio; Domingo, Concepción; Acierno, Domenico; Filippone, Giovanni

2014-05-01

In the present work, two-dimensional systems based on biodegradable polymers such as poly(ɛ-caprolactone) (PCL), poly(ethylene oxide) (PEO) and polylactic acid (PLA) are fabricated by means of a sustainable approach which consists in inducing phase separation in solutions of such polymers and "green" solvents, namely ethyl lactate (EL) and ethyl acetate (EA). The extraction of the solvent is promoted by a controlled drying process, which is performed in either air or supercritical CO2. The latter can indeed act as both an antisolvent, which favors the deposition of the polymer by forming a mixture with EL and EA, and a plasticizing agent, whose solvation and transport properties may considerably affect the microstructure and crystallinity of the polymer films. The morphological, topographical and crystalline properties of the films are tailored through a judicial selection of the materials and the processing conditions and assessed by means of thermal analyses, polarized optical microscopy, scanning electron microscopy and confocal interferometric microscopy. The results show that the morphological and crystalline properties of the films are strongly dependent on the choice of both the polymer/solvent system and the operating conditions during the drying step. In particular, the morphological, topographical and thermal properties of films prepared starting from highly crystalline polymers, namely PCL and PEO, are greatly affected by the crystallization of the material. Conversely, the less crystalline PLA forms almost completely amorphous films.

Dewetting acrylic polymer films with water/propylene carbonate/surfactant mixtures - implications for cultural heritage conservation.

PubMed

Baglioni, M; Montis, C; Brandi, F; Guaragnone, T; Meazzini, I; Baglioni, P; Berti, D

2017-09-13

The removal of hydrophobic polymer films from surfaces is one of the top priorities of modern conservation science. Nanostructured fluids containing water, good solvents for polymers, either immiscible or partially miscible with water, and surfactants have been used in the last decade to achieve controlled removal. The dewetting of the polymer film is often an essential step to achieve efficient removal; however, the role of the surfactant throughout the process is yet to be fully understood. We report on the dewetting of a methacrylate/acrylate copolymer film induced by a ternary mixture of water, propylene carbonate (PC) and C 9-11 E 6 , a nonionic alcohol ethoxylate surfactant. The fluid microstructure was characterised through small angle X-ray scattering and the interactions between the film and water, water/PC and water/PC/C 9-11 E 6 , were monitored through confocal laser-scanning microscopy (CLSM) and analised both from a thermodynamic and a kinetic point of view. The presence of a surfactant is a prerequisite to induce dewetting of μm-thick films at room temperature, but it is not a thermodynamic driver. The amphiphile lowers the interfacial energy between the phases and favors the loss of adhesion of the polymer on glass, decreasing, in turn, the activation energy barrier, which can be overcome by the thermal fluctuations of polymer film stability, initiating the dewetting process.

Refractory Ceramic Foams for Novel Applications

NASA Technical Reports Server (NTRS)

Stackpoole, M.

2008-01-01

Workers at NASA Ames Research center are endeavoring to develop durable, oxidation-resistant, foam thermal protection systems (TPSs) that would be suitable for covering large exterior spacecraft surfaces, would have low to moderate densities, and would have temperature capabilities comparable to those of carbon-based TPSs [reusable at 3,000 F (.1,650 C)] with application of suitable coatings. These foams may also be useful for repairing TPSs while in orbit. Moreover, on Earth as well as in outer space, these foams might be useful as catalyst supports and filters. Preceramic polymers are obvious candidates for use in making the foams in question. The use of these polymers offers advantages over processing routes followed in making conventional ceramics. Among the advantages are the ability to plastically form parts, the ability to form pyrolized ceramic materials at lower temperatures, and the ability to form high-purity microstructures having properties that can be tailored to satisfy requirements. Heretofore, preceramic polymers have been used mostly in the production of such low-dimensional products as fibers because the loss of volatiles during pyrolysis of the polymers leads to porosity and large shrinkage (in excess of 30 percent). In addition, efforts to form bulk structures from preceramic polymers have resulted in severe cracking during pyrolysis. However, because the foams in question would consist of networks of thin struts (in contradistinction to nonporous dense solids), these foams are ideal candidates for processing along a preceramic-polymer route.

Design of polymer motifs for nucleic acid recognition and assembly stabilization

NASA Astrophysics Data System (ADS)

Zhou, Zhun

This dissertation describes the synthesis and assembly of bio-functional polymers and the applications of these polymers to drug encapsulation, delivery, and multivalent biomimetic macromolecular recognition between synthetic polymer and nucleic acids. The main content is divided into three parts: (1) polyacidic domains as strongly stabilizing design elements for aqueous phase polyacrylate diblock assembly; (2) small molecule/polymer recognition triggered macromolecular assembly and drug encapsulation; (3) trizaine derivatized polymer as a novel class of "bifacial polymer nucleic acid" (bPoNA) and applications of bPoNA to nanoparticle loading of DNA/RNA, silencing delivery as well as control of aptamer function. Through the studies in part (1) and part (2), it was demonstrated that well-designed polymer motifs are not only able to enhance assemblies driven by non-specific hydrophobic effect, but are also able to direct assemblies based on specific recognitions. In part (3) of this dissertation, this concept was further extended by the design of polyacrylate polymers that are capable of discrete and robust hybridization with nucleic acids. This surprising finding demonstrated both fundamental and practical applications. Overall, these studies provided insights into the rational design elements for improving the bio-functions of synthetic polymers, and significantly expanded the scope of biological applications in which polymers synthesized via controlled radical polymerization may play a role.

Ionic Liquids in Polymer Design: From Energy to Health

DTIC Science & Technology

2016-10-19

SECURITY CLASSIFICATION OF: ACS Symposium: Ionic Liquids in Polymer Design: From Energy to Health at Fall 2015 ACS Meeting in Boston, MA The...combination of ionic liquids and polymers has emerged as an active field of exploration in polymer science, where new materials have be realized for...2016 Final Report: Ionic Liquids in Polymer Design: From Energy to Health The views, opinions and/or findings contained in this report are those of

Microstructure-Based Computational Modeling of Mechanical Behavior of Polymer Micro/Nano Composites

DTIC Science & Technology

2013-12-01

K. ......... 165  Fig. 5.11. Comparison between experimental data and calibrated numerical models for displacement control tests, at three different...displacement control simulation) for all mesh densities for both work-conjugate and non work-conjugate. ........................ 302  Fig. 9.3. Damage...some large deformation experimental tests (and also accepting the non -uniformity of the strain field). In the established well-known theorem for

Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lassinantti Gualtieri, Magdalena, E-mail: magdalena.gualtieri@unimore.it; Romagnoli, Marcello; Pollastri, Simone

2015-01-15

Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for constructionmore » purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.« less

Towards high water permeability in triazine-framework-based microporous membranes for dehydration of ethanol.

PubMed

Tang, Yu Pan; Wang, Huan; Chung, Tai Shung

2015-01-01

The microstructural evolution of a series of triazine framework-based microporous (TFM) membranes under different conditions has been explored in this work. The pristine TFM membrane is in situ fabricated in the course of polymer synthesis via a facile Brønsted-acid-catalyzed cyclotrimerizaiton reaction. The as-synthesized polymer exhibits a microporous network with high thermal stability. The free volume size of the TFM membranes gradually evolved from a unimodal distribution to a bimodal distribution under annealing, as analyzed by positron annihilation lifetime spectroscopy (PALS). The emergence of the bimodal distribution is probably ascribed to the synergetic effect of quenching and thermal cyclization reaction. In addition, the fractional free volume (FFV) of the membranes presents a concave trend with increasing annealing temperature. Vapor sorption tests reveal that the mass transport properties are closely associated with the free volume evolution, which provides an optimal condition for dehydration of biofuels. A promising separation performance with extremely high water permeability has been attained for dehydration of an 85 wt % ethanol aqueous solution at 45 °C. The study on the free volume evolution of the TFM membranes may provide useful insights about the microstructure and mass transport behavior of the microporous polymeric materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Orienting the Microstructure Evolution of Copper Phthalocyanine as an Anode Interlayer in Inverted Polymer Solar Cells for High Performance.

PubMed

Li, Zhiqi; Liu, Chunyu; Zhang, Xinyuan; Li, Shujun; Zhang, Xulin; Guo, Jiaxin; Guo, Wenbin; Zhang, Liu; Ruan, Shengping

2017-09-20

Recent advances in the interfacial modification of inverted-type polymer solar cells (PSCs) have resulted from controlling the surface energy of the cathode-modified layer (TiO 2 or ZnO) to enhance the short-circuit current (J sc ) or optimizing the contact morphology of the cathode (indium tin oxide or fluorine-doped tin oxide) and active layer to increase the fill factor. Herein, we report that the performance enhancement of PSCs is achieved by incorporating a donor macromolecule copper phthalocyanine (CuPc) as an anode modification layer. Using the approach based on orienting the microstructure evolution, uniformly dispersed island-shaped CuPc spot accumulations are built on the top of PTB7:PC 71 BM blend film, leading to an efficient spectral absorption and photogenerated exciton splitting. The best power conversion efficiency of PSCs is increased up to 9.726%. In addition to the enhanced light absorption, the tailored anode energy level alignment and optimized boundary morphology by incorporating the CuPc interlayer boost charge extraction efficiency and suppress the interfacial molecular recombination. These results demonstrate that surface morphology induction through molecular deposition is an effective method to improve the performance of PSCs, which reveals the potential implications of the interlayer between the organic active layer and the electrode buffer layer.

Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

PubMed

Wang, XinJie; Wu, YanQing; Huang, FengLei

2017-01-05

A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Achieving ICME with Multiscale Modeling: The Effects of Constituent Properties and Processing on the Performance of Laminated Polymer Matrix Composite Structures

NASA Technical Reports Server (NTRS)

Pineda, Evan Jorge; Bednarcyk, Brett A.; Arnold, Steven M.

2014-01-01

Integrated computational materials engineering (ICME) is a useful approach for tailoring the performance of a material. For fiber-reinforced composites, not only do the properties of the constituents of the composite affect the performance, but so does the architecture (or microstructure) of the constituents. The generalized method of cells is demonstrated to be a viable micromechanics tool for determining the effects of the microstructure on the performance of laminates. The micromechanics is used to predict the inputs for a macroscale model for a variety of different fiber volume fractions, and fiber architectures. Using this technique, the material performance can be tailored for specific applications by judicious selection of constituents, volume fraction, and architectural arrangement given a particular manufacturing scenario

Effect of trap states and microstructure on charge carrier conduction mechanism through semicrystalline poly(vinyl alcohol) granular film

NASA Astrophysics Data System (ADS)

Das, A. K.; Bhowmik, R. N.; Meikap, A. K.

2018-05-01

We report a comprehensive study on hysteresis behaviour of current-voltage characteristic and impedance spectroscopy of granular semicrystalline poly(vinyl alcohol) (PVA) film. The charge carrier conduction mechanism and charge traps of granular PVA film by measuring and analyzing the temperature dependent current-voltage characteristic indicate a bi-stable electronic state in the film. A sharp transformation of charge carrier conduction mechanism from Poole-Frenkel emission to space charge limited current mechanism has been observed. An anomalous oscillatory behaviour of current has been observed due to electric pulse effect on the molecular chain of the polymer. Effect of microstructure on charge transport mechanism has been investigated from impedance spectroscopy analysis. An equivalent circuit model has been proposed to explain the result.

Synthesis of inorganic polymers using fly ash and primary lead slag.

PubMed

Onisei, S; Pontikes, Y; Van Gerven, T; Angelopoulos, G N; Velea, T; Predica, V; Moldovan, P

2012-02-29

The present work reports on the synthesis and properties of inorganic polymers ("geopolymers") made of 100% fly ash from lignite's combustion, 100% primary lead slag and mixtures of the two. In the inorganic polymers with both fly ash and lead slag the main crystalline phases detected are wüstite, magnetite, sodium zinc silicate, quartz, anorthite, and gehlenite; litharge partially dissolves. FTIR analysis in these samples revealed that the main peaks and bands of end members also exist, along with a new amorphous reaction product. In terms of microstructure, both fly ash and lead slag dissolve and contribute in the binding phase whereas the larger particles act as aggregates. For an increasing lead slag in the composition, the binding phase is changing in chemistry and reaches PbO values higher than 50 wt.% for the 100% lead slag inorganic polymer. Regarding the properties of fly ash and lead slag inorganic polymers, compressive strength is higher than 35 MPa in all cases and water absorption diminishes as the lead slag content increases. A comparison of leaching results before and after polymerisation reveals that pH is an important factor as Pb is immobilised in the binding phase, unlike Zn and As. Copyright © 2011 Elsevier B.V. All rights reserved.

Cell-matrix mechanical interaction in electrospun polymeric scaffolds for tissue engineering: Implications for scaffold design and performance.

PubMed

Kennedy, Kelsey M; Bhaw-Luximon, Archana; Jhurry, Dhanjay

2017-03-01

Engineered scaffolds produced by electrospinning of biodegradable polymers offer a 3D, nanofibrous environment with controllable structural, chemical, and mechanical properties that mimic the extracellular matrix of native tissues and have shown promise for a number of tissue engineering applications. The microscale mechanical interactions between cells and electrospun matrices drive cell behaviors including migration and differentiation that are critical to promote tissue regeneration. Recent developments in understanding these mechanical interactions in electrospun environments are reviewed, with emphasis on how fiber geometry and polymer structure impact on the local mechanical properties of scaffolds, how altering the micromechanics cues cell behaviors, and how, in turn, cellular and extrinsic forces exerted on the matrix mechanically remodel an electrospun scaffold throughout tissue development. Techniques used to measure and visualize these mechanical interactions are described. We provide a critical outlook on technological gaps that must be overcome to advance the ability to design, assess, and manipulate the mechanical environment in electrospun scaffolds toward constructs that may be successfully applied in tissue engineering and regenerative medicine. Tissue engineering requires design of scaffolds that interact with cells to promote tissue development. Electrospinning is a promising technique for fabricating fibrous, biomimetic scaffolds. Effects of electrospun matrix microstructure and biochemical properties on cell behavior have been extensively reviewed previously; here, we consider cell-matrix interaction from a mechanical perspective. Micromechanical properties as a driver of cell behavior has been well established in planar substrates, but more recently, many studies have provided new insights into mechanical interaction in fibrillar, electrospun environments. This review provides readers with an overview of how electrospun scaffold mechanics and cell behavior work in a dynamic feedback loop to drive tissue development, and discusses opportunities for improved design of mechanical environments that are conducive to tissue development. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

N-vinylpyrrolidone modified glass-ionomer resins for improved dental restoratives

NASA Astrophysics Data System (ADS)

Xie, Dong

The studies described in this dissertation focus on improvement of mechanical properties of current glass-ionomer cements. Thermal properties and microstructures of the cements were correlated with their mechanical strengths. The first study evaluated mechanical properties of selected commercial glass-ionomer cements and examined their microstructures. The results showed that resin-modified glass-ionomer cements (RM GICs) exhibited much higher flexural (FS) and diametral tensile strengths (DTS), compared to conventional GICs (C GICs). In addition, they exhibited comparable compressive strength (CS), relatively low microhardness and less wear resistance than C GICs. The C GICs exhibited brittle behavior, whereas the RM GICs underwent substantial plastic deformation in compression. The mechanical properties of the GICs were closely related to their microstructures. Factors such as the density of the microstructure, the integrity of the interface between the glass particles and polymer matrix, particle size and the number and size of voids have important roles in determining the mechanical properties. The second study evaluated thermal properties of these GICs. The results showed that the RM GICs exhibited higher thermal transition temperatures than those of the C GICs, thermal expansion coefficients of these cements were close to those of human teeth, and the indentation creep of the RM GICs were higher than the C GICs. The third study explored and evaluated the effect of a water-soluble monomer, N-vinylpyrrolidone (NVP), on the performance of current C GICs, indicating a significant improvement in both mechanical and working properties. The fourth study demonstrated the process of determining the optimal molar ratio of the NVP-containing copolymers, using design of experiment. The results showed that the optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on the FS test. The molar ratio of 8:2:1 (AA:IA:NVP) was considered as the best molar ratio for these copolymers, based on the DTS and CS tests. The fifth study formulated the NVP-containing RM GICs using a statistical design of experiment. The results indicated that the best graft ratio for 2-isocyanatoethyl methacrylate (IEM) in this system was 15% of the terpolymer by a molar ratio. The optimal formulation was found to be at the weight ratio of 55:15:30 (RM NVP-containing terpolymer: 2-hydroxyethyl methacrylate (HEMA): Hsb2O). Stress-strain curves showed that a relatively high amount of water in the formulation led to higher elastic modulus and proportional limit and lower malleability, whereas a relatively high amount of HEMA gave the opposite results. The sixth study evaluated the NVP modified GICs (NVPM GICs) with the best molar ratios and optimal formulations in the mechanical, thermal and working properties. The results showed that the effect of molecular weight on mechanical properties of the NVPM GICs were evident. Different glass powders exhibited different effects on properties of the NVPM GICs, due to different compositions, size and affinity. Powder/liquid ratios had significant effects on the mechanical properties of NVPM GICs, especially on FS. P/W ratios are only beneficial to the NVPM GICs mixed with the Fuji II glass powders. The NVPM GICs showed a higher WT than the models, due to water retention of the NVP ring. Thermal expansion coefficients for the NVPM GICs were close to those for the natural tooth. Mismatch between the glass powders used and the polymer matrix was a big concern in this study and should be solved in the future.

Diketopyrrolopyrrole Polymers with Thienyl and Thiazolyl Linkers for Application in Field-Effect Transistors and Polymer Solar Cells.

PubMed

Yu, Yaping; Wu, Yang; Zhang, Andong; Li, Cheng; Tang, Zheng; Ma, Wei; Wu, Yonggang; Li, Weiwei

2016-11-09

Conjugated polymers consisting of diketopyrrolopyrrole (DPP) units have been successfully applied in field-effect transistors (FETs) and polymer solar cells (PSCs), while most of the DPP polymers were designed as symmetric structures containing identical aromatic linkers. In this manuscript, we design a new asymmetric DPP polymer with varied aromatic linkers in the backbone for application in FETs and PSCs. The designation provides the chance to finely adjust the energy levels of conjugated polymers so as to influence the device performance. The asymmetric polymer exhibits highly crystalline properties, high hole mobilities of 3.05 cm 2 V -1 s -1 in FETs, and a high efficiency of 5.9% in PSCs with spectra response from 300 to 850 nm. Morphology investigation demonstrates that the asymmetric polymer has a large crystal domain in blended thin films, indicating that the solar cell performance can be further enhanced by optimizing the microphase separation. The study reveals that the asymmetric design via adjusting the aromatic linkers in DPP polymers is a useful route toward flexible electronic devices.

Rapid production of polymer microstructures

NASA Astrophysics Data System (ADS)

Nagarajan, Pratapkumar

The goal of this research is to develop an integrated polymer embossing module, with which difficult-to-emboss polymer microstructures and microparts can be fabricated in a cost-effective manner. In particular, the research addresses three major limitations of the hot embossing process, namely, long cycle time, difficulty in producing shell patterns, and difficulty in building up a high embossing pressure on thick substrates. To overcome these limitations, three new technical approaches - two-station embossing, rubber-assisted embossing, and through-thickness embossing - were developed and investigated. Fundamental understanding of these new embossing techniques were achieved through extensive experimental and theoretical studies involving parametric experiments, rheological characterization, surface investigation, mathematical modeling, and computer simulation. A two-station embossing process was developed to reduce the hot embossing cycle time, accomplished by decoupling the heating and cooling stations. For this purpose, the standard hot embossing mold was replaced by a shell type mold, and separate hot and cold stations were used to selectively heat and cool the shell mold during the process. With this method, microlens arrays and micro channels were fabricated onto ABS and HDPE substrates with a cycle time of approximately 10 s. Numerical simulations were performed to study the effect of different design parameters, including thermal contact resistance, shell material and shell thickness, on the thermal response at the mold surface. Furthermore, the polymer flow during the two-station embossing process for the microlens was numerically studied. The simulated filling behavior agreed with the experimental observation, and the predicted thermal and deformation history of the polymer offers a good explanation on the experimentally observed process characteristics. The second technique, rubber-assisted embossing, involving a rubber pad as a soft counter tool, was developed for precision embossing of shell structures. The rubber pad acted as a temporary negative during embossing and recovered to its original geometry after mold opening. With rubber-assisted embossing, a micro shell pattern with a characteristic size of 50 mum was successfully patterned on 25-mum thick polystyrene films. A focused study was undertaken on rubber-assisted isothermal embossing to establish the relationship between process parameters and pattern replication. It was found that the pattern replication and film uniformity were affected by the embossing temperature and the hardness of rubber. It was also found that adequate plasticity and higher stiffness of the deforming film were essential in achieving excellent pattern replication and uniformity in film thickness. The through-thickness embossing process was developed for embossing pressure buildup and fabrication of 3-D parts. The embossing tool includes a punching head and to-be-replicated features in the socket behind the punching head. The built-in punching head facilitates a through-thickness action and provides a close-die environment for embossing pressure buildup. The method was used to emboss multichannel millimeter waveguides which requires crispy edges and accurate dimensions. With a tool temperature of 140°C, an embossing time of 3 min and a total cycle time of 7 min, discrete 4-channel waveguides were successfully embossed from a room-temperature ABS substrate. A computer model was established to study the flow behavior during through-thickness embossing. It was found that nonisothermal embossing conditions helped to confine the polymer in the cavity and reduce the outflow into the surrounding region, thus achieving complete fill of the cavity.

Progress on CD-DVD laser microfabrication method to develop cell culture scaffolds integrating biomimetic characteristics

NASA Astrophysics Data System (ADS)

Hautefeuille, Mathieu; Vázquez-Victorio, Genaro; Cruz-Ramírez, Aaron; Cabriales, Lucia; Jiménez-Diaz, Edgar; Escutia-Guadarrama, Lidia; López-Aparicio, Jehú; Pérez-Calixto, Daniel; Cano-Jorge, Mariel; Nieto-Rivera, Brenda; Sánchez-Olvera, Raúl

2018-02-01

The development of organ-on-chip and biological scaffolds is currently requiring simpler methods to microstructure biocompatible materials in three dimensions, fabricate structural and functional elements in biomaterials or modify the physicochemical properties of desired substrates. With the aim of creating simple, cost-effective alternatives to conventional existing techniques to produce such platforms with very specific properties, a low-power CD-DVD laser pickup head was recycled and mounted on a programmable three-axis micro-displacement system in order to modify the surface of polymeric materials in a local fashion. Thanks to a specially-designed method using a strongly absorbing additive coating the materials of interest, it has been possible to establish and precisely control processes useful in microtechnology for biomedical applications and normally restricted to much less affordable high-power lasers. In this work, we present our latest progress regarding the application of our fabrication technique to the development of organ-on-chip platforms thanks to the simple integration of several biomimetic characteristics typically achieved with traditional, less cost-effective microtechnology methods in one step or through replica-molding. Our straightforward approach indeed enables great control of local laser microablation for true on-demand biomimetic micropatterned designs in several transparent polymers and hydrogels of tunable stiffness and is allowing integration of microfluidics, microelectronics, optical waveguides, surface microstructuring and even transfer of superficial protein micropatterns on a variety of biocompatible materials. The results presented here were validated using hepatic and fibroblasts cell lines to demonstrate the viability of our procedure for organ-on-chip development and show the impact of such features in cell culture.

Computational Design for Multifunctional Microstructural Composites

NASA Astrophysics Data System (ADS)

Chen, Yuhang; Zhou, Shiwei; Li, Qing

As an important class of natural and engineered materials, periodic microstructural composites have drawn substantial attention from the material research community for their excellent flexibility in tailoring various desirable physical behaviors. To develop periodic cellular composites for multifunctional applications, this paper presents a unified design framework for combining stiffness and a range of physical properties governed by quasi-harmonic partial differential equations. A multiphase microstructural configuration is sought within a periodic base-cell design domain using topology optimization. To deal with conflicting properties, e.g. conductivity/permeability versus bulk modulus, the optimum is sought in a Pareto sense. Illustrative examples demonstrate the capability of the presented procedure for the design of multiphysical composites and tissue scaffolds.

Analysis of sintered polymer scaffolds using concomitant synchrotron computed tomography and in situ mechanical testing.

PubMed

Dhillon, A; Schneider, P; Kuhn, G; Reinwald, Y; White, L J; Levchuk, A; Rose, F R A J; Müller, R; Shakesheff, K M; Rahman, C V

2011-12-01

The mechanical behaviour of polymer scaffolds plays a vital role in their successful use in bone tissue engineering. The present study utilised novel sintered polymer scaffolds prepared using temperature-sensitive poly(DL-lactic acid-co-glycolic acid)/poly(ethylene glycol) particles. The microstructure of these scaffolds was monitored under compressive strain by image-guided failure assessment (IGFA), which combined synchrotron radiation computed tomography (SR CT) and in situ micro-compression. Three-dimensional CT data sets of scaffolds subjected to a strain rate of 0.01%/s illustrated particle movement within the scaffolds with no deformation or cracking. When compressed using a higher strain rate of 0.02%/s particle movement was more pronounced and cracks between sintered particles were observed. The results from this study demonstrate that IGFA based on simultaneous SR CT imaging and micro-compression testing is a useful tool for assessing structural and mechanical scaffold properties, leading to further insight into structure-function relationships in scaffolds for bone tissue engineering applications.

Free Volume Structure of Acrylic-Type Dental Nanocomposites Tested with Annihilating Positrons.

PubMed

Shpotyuk, Olha; Ingram, Adam; Shpotyuk, Oleh

2016-12-01

Positron annihilation spectroscopy in lifetime measuring mode exploring conventional fast-fast coincidence ORTEC system is employed to characterize free volume structure of commercially available acrylic-type dental restorative composite Charisma® (Heraeus Kulzer GmbH, Germany). The measured lifetime spectra for uncured and light-cured composites are reconstructed from unconstrained x3-term fitting and semi-empirical model exploring x3-x2-coupling decomposition algorithm. The governing channel of positron annihilation in the composites studied is ascribed to mixed positron-Ps trapping, where Ps decaying in the third component is caused entirely by input from free-volume holes in polymer matrix, while the second component is defined by free positron trapping in interfacial free-volume holes between filler nanoparticles and surrounded polymer matrix. Microstructure scenario of the photopolymerization shrinkage includes cross-linking of structural chains in polymer matrix followed by conversion of bound positron-electron (positronium) traps in positron-trapping interfacial free-volume voids in a vicinity of agglomerated filler nanoparticles.

Self-organization of glucose oxidase-polymer surfactant nanoconstructs in solvent-free soft solids and liquids.

PubMed

Sharma, Kamendra P; Zhang, Yixiong; Thomas, Michael R; Brogan, Alex P S; Perriman, Adam W; Mann, Stephen

2014-10-02

An anisotropic glucose oxidase-polymer surfactant nanoconjugate is synthesized and shown to exhibit complex temperature-dependent phase behavior in the solvent-free state. At close to room temperature, the nanoconjugate crystallizes as a mesolamellar soft solid with an expanded interlayer spacing of ca. 12 nm and interchain correlation lengths consistent with alkyl tail-tail and PEO-PEO ordering. The soft solid displays a birefringent spherulitic texture and melts at 40 °C to produce a solvent-free liquid protein without loss of enzyme secondary structure. The nanoconjugate melt exhibits a birefringent dendritic texture below the conformation transition temperature (Tc) of glucose oxidase (58 °C) and retains interchain PEO-PEO ordering. Our results indicate that the shape anisotropy of the protein-polymer surfactant globular building block plays a key role in directing mesolamellar formation in the solvent-free solid and suggests that the microstructure observed in the solvent-free liquid protein below Tc is associated with restrictions in the intramolecular motions of the protein core of the nanoconjugate.

Preparation and characterization of functional material based on hybrid polymer composites

NASA Astrophysics Data System (ADS)

Agusu, La; Amiruddin; Taswito, Chen Chen; Herdianto; Zamrun, Muh.

2016-08-01

The microstructures and properties of hybrid polymer composites based on polyaniline (PANi)/γ-Fe2O3 nanoparticles/TiO2/carbon have been investigated for multifunctional applications such as heavy metal removal and initial study for radar absorbing material application. γ-Fe2O3 nanoparticles with spherical shape were synthetized by a coprecipitation method from iron sand. By activating the polyethylene glycol (PEG-400) coated carbon of coconut shell, the homogenous shape and size of carbon was achieved. Then, γ- Fe2O3, TiO2, and carbon were mixed with PANi by an in situ polymerization method at low temperature 0-5 oC. Characterization process involved XRD, SEM, FTIR, VSM, and DC conductivity measurements. For radar absorber application, the functionalized polymer composites showed good electrical conductivity 0.45 S/cm to absorb the incoming electromagnetic energy. An efficient and effective reduction of Pb2+ ion from the water has been achieved by using this material.

Toughening and functionalization of bioactive ceramic and glass bone scaffolds by biopolymer coatings and infiltration: a review of the last 5 years.

PubMed

Philippart, Anahí; Boccaccini, Aldo R; Fleck, Claudia; Schubert, Dirk W; Roether, Judith A

2015-01-01

Inorganic scaffolds with high interconnected porosity based on bioactive glasses and ceramics are prime candidates for applications in bone tissue engineering. These materials however exhibit relatively low fracture strength and high brittleness. A simple and effective approach to improve the toughness is to combine the basic scaffold structure with polymer coatings or through the formation of interpenetrating polymer-bioactive ceramic microstructures. The polymeric phase can additionally serve as a carrier for growth factors and therapeutic drugs, thus adding biological functionalities. The present paper reviews the state-of-the art in the field of polymer coated and infiltrated bioactive inorganic scaffolds. Based on the notable combination of bioactivity, improved mechanical properties and drug or growth factor delivery capability, this scaffold type is a candidate for bone and osteochondral regeneration strategies. Remaining challenges for the improvement of the materials are discussed and opportunities to broaden the application potential of this scaffold type are also highlighted.

Mechanical Behavior of a Hi-Nicalon(tm)/SiC Composite Having a Polycarbosilane Derived Matrix

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.; Calomino, Anthony M.; McCue, Terry R.

1999-01-01

Polymer infiltration of a rigidized preform, followed by pyrolysis to convert the polymer to a ceramic, potentially offers a lower cost alternative to CVD. It also offers more moderate temperature requirements than melt infiltration approaches, which should minimize potential fiber damage during processing. However, polymer infiltration and pyrolysis results in a more microcracked matrix. Preliminary mechanical property characterization, including elevated temperature (1204 C) tensile, 500 h stress rupture behavior and low cycle fatigue, was conducted on Hi-Nicalon (TM)/Si-C-(O) composites having a dual layer BN/SiC interface and a matrix derived by impregnation and pyrolysis of allylhydridopolycarbosilane (AHPCS). Microstructural evaluation of failure surfaces and of polished transverse and longitudinal cross sections of the failed specimens was used to identify predominant failure mechanisms. In stress rupture testing at 1093 C, the failure was interface dominated, while at 1204 C in both stress rupture and two hour hold/fatigue tests failure was matrix dominated, resulting in specimen delamination.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larson, Natalie M.; Zok, Frank W.

One route for producing fiber-reinforced ceramic-matrix composites entails repeated impregnation and pyrolysis of a preceramic polymer in a fiber preform. The process relies crucially on the development of networks of contiguous cracks during pyrolysis, thereby allowing further impregnation to attain nearly-full densification. The present study employs in-situ x-ray computed tomography (XCT) to reveal in three dimensions the evolution of matrix structure during pyrolysis of a SiC-based preceramic polymer to 1200 °C. Observations are used to guide the development of a taxonomy of crack geometries and crack structures and to identify the temporal sequence of their formation. A quantitative analysis ismore » employed to characterize effects of local microstructural dimensions on the conditions required to form cracks of various types. Complementary measurements of gas evolution and mass loss of the preceramic polymer during pyrolysis as well as changes in mass density and Young's modulus provide context for the physical changes revealed by XCT. Furthermore, the findings provide a foundation for future development of physics-based models to guide composite fabrication processes.« less

Recent Advances in Gas Barrier Thin Films via Layer-by-Layer Assembly of Polymers and Platelets.

PubMed

Priolo, Morgan A; Holder, Kevin M; Guin, Tyler; Grunlan, Jaime C

2015-05-01

Layer-by-layer (LbL) assembly has emerged as the leading non-vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide-based barrier films. This Feature Article is a mini-review of LbL-based multilayer thin films with a 'nanobrick wall' microstructure comprising polymeric mortar and nano-platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water-based thin films exhibit oxygen transmission rates below 5 × 10(-3) cm(3) m(-2) day(-1) atm(-1) and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake-filled polymers are briefly reviewed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An analysis of FtsZ assembly using small angle X-ray scattering and electron microscopy.

PubMed

Kuchibhatla, Anuradha; Abdul Rasheed, A S; Narayanan, Janaky; Bellare, Jayesh; Panda, Dulal

2009-04-09

Small angle X-ray scattering (SAXS) was used for the first time to study the self-assembly of the bacterial cell division protein, FtsZ, with three different additives: calcium chloride, monosodium glutamate and DEAE-dextran hydrochloride in solution. The SAXS data were analyzed assuming a model form factor and also by a model-independent analysis using the pair distance distribution function. Transmission electron microscopy (TEM) was used for direct observation of the FtsZ filaments. By sectioning and negative staining with glow discharged grids, very high bundling as well as low bundling polymers were observed under different assembly conditions. FtsZ polymers formed different structures in the presence of different additives and these additives were found to increase the bundling of FtsZ protofilaments by different mechanisms. The combined use of SAXS and TEM provided us a significant insight of the assembly of FtsZ and microstructures of the assembled FtsZ polymers.

Positron lifetime spectroscopy for investigation of thin polymer coatings

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Sprinkle, Danny R.; Eftekhari, Abe

1993-01-01

In the aerospace industry, applications for polymer coatings are increasing. They are now used for thermal control on aerospace structures and for protective insulating layers on optical and microelectronic components. However, the effectiveness of polymer coatings depends strongly on their microstructure and adhesion to the substrates. Currently, no technique exists to adequately monitor the quality of these coatings. We have adapted positron lifetime spectroscopy to investigate the quality of thin coatings. Results of measurements on thin (25-micron) polyurethane coatings on aluminum and steel substrates have been compared with measurements on thicker (0.2-cm) self-standing polyurethane discs. In all cases, we find positron lifetime groups centered around 560 psec, which corresponds to the presence of 0.9-A(exp 3) free-volume cells. However, the number of these free-volume cells in thin coatings is larger than in thick discs. This suggests that some of these cells may be located in the interfacial regions between the coatings and the substrates. These results and their structural implications are discussed in this report.

Energy Storage Publications | Transportation Research | NREL

Science.gov Websites

. 367, 1 November 2017 pp. 214-215. Quantitative Microstructure Characterization of a NMC Electrode . NREL/PR-5400-68759. Quantitative Microstructure Characterization of a NMC Electrode Presentation Source . NREL/PR-5400-68339. Microstructure Characterization and Modeling for Improved Electrode Design

Microstructure-tunable highly conductive graphene-metal composites achieved by inkjet printing and low temperature annealing

NASA Astrophysics Data System (ADS)

Zhao, Jie; Song, Man; Wen, Chenyu; Majee, Subimal; Yang, Dong; Wu, Biao; Zhang, Shi-Li; Zhang, Zhi-Bin

2018-03-01

We present a method for fabricating highly conductive graphene-silver composite films with a tunable microstructure achieved by means of an inkjet printing process and low temperature annealing. This is implemented by starting from an aqueous ink formulation using a reactive silver solution mixed with graphene nanoplatelets (GNPs), followed by inkjet printing deposition and annealing at 100 °C for silver formation. Due to the hydrophilic surfaces and the aid of a polymer stabilizer in an aqueous solution, the GNPs are uniformly covered with a silver layer. Simply by adjusting the content of GNPs in the inks, highly conductive GNP/Ag composites (>106 S m-1), with their microstructure changed from a large-area porous network to a compact film, is formed. In addition, the printed composite films show superior quality on a variety of unconventional substrates compared to its counterpart without GNPs. The availability of composite films paves the way to the metallization in different printed devices, e.g. interconnects in printed circuits and electrodes in energy storage devices.

A Highly Sensitive Resistive Pressure Sensor Based on a Carbon Nanotube-Liquid Crystal-PDMS Composite.

PubMed

Pan, Jin; Liu, Shiyu; Yang, Yicheng; Lu, Jiangang

2018-06-08

Resistive pressure sensors generally employ microstructures such as pores and pyramids in the active layer or on the electrodes to reduce the Young’s modulus and improve the sensitivity. However, such pressure sensors always exhibit complex fabrication process and have difficulties in controlling the uniformity of microstructures. In this paper, we demonstrated a highly sensitive resistive pressure sensor based on a composite comprising of low-polarity liquid crystal (LPLC), multi-walled carbon nanotube (MWCNT), and polydimethylsiloxane (PDMS) elastomer. The LPLC in the PDMS forms a polymer-dispersed liquid crystal (PDLC) structure which can not only reduce the Young’s modulus but also contribute to the construction of conductive paths in the active layer. By optimizing the concentration of LC in PDMS elastomer, the resistive pressure sensor shows a high sensitivity of 5.35 kPa −1 , fast response (<150 ms), and great durability. Fabrication process is also facile and the uniformity of the microstructures can be readily controlled. The pressure sensor offers great potential for applications in emerging wearable devices and electronic skins.

Microstructure and Thermal Conductivity of Carbon Nanotube Reinforced Cu Composites.

PubMed

Chen, Pingan; Zhang, Jian; Shen, Qiang; Luo, Guoqiang; Dai, Yang; Wang, Chuanbing; Li, Meijuan; Zhang, Lianmeng

2017-04-01

Microstructure and thermal conductivity (TC) of carbon nanotubes reinforced Cu (CNT-Cu) composites have been studied. When CNTs were coated with nano Cu by electroless plating, the TC of CNT-Cu composites showed a noticeable improvement and increased with CNT contents. When 1.0 vol% CNTs was added, the TC of CNT-Cu composites increased to 420.4 W/(m · K), 30% higher than that of monolithic Cu (323.1 W/(m · K)). According to the measured TC of CNT-Cu composites, the interfacial thermal resistance of CNT-Cu composites was calculated as 3.0 × 10⁻⁹ m² K/W which was lower than the reported values of CNTs reinforced polymer matrix composites and ceramic matrix composites. Microstructures showed that CNTs modified with nano Cu were homogeneously dispersed and embedded in the Cu matrix, indicating that there was strong bonding between CNTs and Cu. The homogeneously dispersed CNTs and reduction of interfacial thermal resistance resulted in the improvement of thermal conductivity of CNT-Cu composites. Therefore, the prepared CNT-Cu composites are promising materials for thermal management applications.

``Effect of Polyalkylthiophene Microstructure on Physical and Optoelectronic Properties''

NASA Astrophysics Data System (ADS)

Minkler, Michael J., Jr.; Beckingham, Bryan S.

Conjugated polymers have been of widespread interest as flexible semiconductors for organic electronic devices such as solar cells, field effect transistor,s and light-emitting diodes. Of particular interest have been alkyl-substituted polythiophenes due to their well-controlled synthesis, favorable optoelectronic properties, and solubility in organic solvents. Importantly, relatively small changes to the chemical microstructure in poly(3-alkylthiophenes) (P3ATs) can have a significant effect on the resulting physical and optoelectronic properties. For instance, the addition of aliphatic side chains onto unsubstituted polythiophene provides solubility but also greatly decreases conductivity in comparison to unsubstituted polythiophene (PT). In this work, we use Grignard metathesis polymerization to synthesize poly(3-hexylthiophene) (P3HT), PT, and statistical copolymers (P[3HT-co-T]) over a range of compositions. We examine the physical properties (melting temperature, crystallinity, etc) by differential scanning calorimetry and wide angle X-ray scattering, optoelectronic properties by UV/Vis spectroscopy, and solubility in organic solvents of these copolymers in order to gain insights into the interplay of microstructure and properties in this class of materials.

Silicon and aluminum doping effects on the microstructure and properties of polymeric amorphous carbon films

NASA Astrophysics Data System (ADS)

Liu, Xiaoqiang; Hao, Junying; Xie, Yuntao

2016-08-01

Polymeric amorphous carbon films were prepared by radio frequency (R.F. 13.56 MHz) magnetron sputtering deposition. The microstructure evolution of the deposited polymeric films induced by silicon (Si) and aluminum(Al) doping were scrutinized through infrared spectroscopy, multi-wavelength Raman spectroscopy, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The comparative results show that Si doping can enhance polymerization and Al doping results in an increase in the ordered carbon clusters. Si and Al co-doping into polymeric films leads to the formation of an unusual dual nanostructure consisting of cross-linked polymer-like hydrocarbon chains and fullerene-like carbon clusters. The super-high elasticity and super-low friction coefficients (<0.002) under a high vacuum were obtained through Si and Al co-doping into the films. Unconventionally, the co-doped polymeric films exhibited a superior wear resistance even though they were very soft. The relationship between the microstructure and properties of the polymeric amorphous carbon films with different elements doping are also discussed in detail.

Microstructural controls on the viscoplasticity of Carbopol, and possible applications to shale deformation studies

NASA Astrophysics Data System (ADS)

Hayman, N. W.; Shafiei, M.; Balhoff, M.; Daigle, H.

2017-12-01

To a first order, sedimentary materials behave in an elastic-plastic manner for most experimental and natural conditions at short time scales. However, long-term patterns of leakage from carbon-capture and storage efforts, and reduced efficiency during unconventional hydrocarbon production, point to a broader range of subsurface behaviors. Our analyses of microstructural and porosity responses to experimental deformation of shale suggest that sedimentary rock deformation is not strictly elastic-plastic. For example, organic matter (OM) in mudrocks can fracture during failure, but elsewhere may be more viscous in the same rock volume. The fracture of OM can be accompanied by some combination of frictional and poroelastic deformation in the surrounding clay aggregates, potentially described by critical-state-line soil mechanics. What is less clear is the possible role of viscoplasticity in sedimentary rock deformation. Though not a good analog material for all rock deformation, the cross-linked polymer Carbopol provides an excellent opportunity to explore controls on viscoplasticity. Above the yield stress, carbopol plastic deformation follows a Herschel-Bulkley model wherein shear stress varies as function of strain rate to a power that is generally <1; i.e. it is a shear-thinning material. The rheology can then be tuned by changing the pH of the gel. Using images obtained from scanning electron microscopy, including using a cryogenic system, we found that a structural transition from a dilute neutralized dispersion to an aggregate of closely packed particulates occurs as the pH of the polymer solution increases. This closely packed microstructure thus controls the yield strength which in turn follows approximately a non-linear relationship with porosity. This "analog material" thus has allowed us to quantify the microstructural length-scales that govern viscoplasticity in this material. Future experiments and numerical modeling can evaluate if a viscoplastic component to sedimentary rock deformation is important during engineering efforts. Such an exploration might focus on porosity-yield stress relationships and the monitoring fracture propagation for a wide range of stress conditions, including those which enhance ductility.

Shape-Memory Hydrogels: Evolution of Structural Principles To Enable Shape Switching of Hydrophilic Polymer Networks.

PubMed

Löwenberg, Candy; Balk, Maria; Wischke, Christian; Behl, Marc; Lendlein, Andreas

2017-04-18

The ability of hydrophilic chain segments in polymer networks to strongly interact with water allows the volumetric expansion of the material and formation of a hydrogel. When polymer chain segments undergo reversible hydration depending on environmental conditions, smart hydrogels can be realized, which are able to shrink/swell and thus alter their volume on demand. In contrast, implementing the capacity of hydrogels to switch their shape rather than volume demands more sophisticated chemical approaches and structural concepts. In this Account, the principles of hydrogel network design, incorporation of molecular switches, and hydrogel microstructures are summarized that enable a spatially directed actuation of hydrogels by a shape-memory effect (SME) without major volume alteration. The SME involves an elastic deformation (programming) of samples, which are temporarily fixed by reversible covalent or physical cross-links resulting in a temporary shape. The material can reverse to the original shape when these molecular switches are affected by application of a suitable stimulus. Hydrophobic shape-memory polymers (SMPs), which are established with complex functions including multiple or reversible shape-switching, may provide inspiration for the molecular architecture of shape-memory hydrogels (SMHs), but cannot be identically copied in the world of hydrophilic soft materials. For instance, fixation of the temporary shape requires cross-links to be formed also in an aqueous environment, which may not be realized, for example, by crystalline domains from the hydrophilic main chains as these may dissolve in presence of water. Accordingly, dual-shape hydrogels have evolved, where, for example, hydrophobic crystallizable side chains have been linked into hydrophilic polymer networks to act as temperature-sensitive temporary cross-links. By incorporating a second type of such side chains, triple-shape hydrogels can be realized. Considering the typically given light permeability of hydrogels and the fully hydrated state with easy permeation by small molecules, other types of stimuli like light, pH, or ions can be employed that may not be easily used in hydrophobic SMPs. In some cases, those molecular switches can respond to more than one stimulus, thus increasing the number of opportunities to induce actuation of these synthetic hydrogels. Beyond this, biopolymer-based hydrogels can be equipped with a shape switching function when facilitating, for example, triple helix formation in proteins or ionic interactions in polysaccharides. Eventually, microstructured SMHs such as hybrid or porous structures can combine the shape-switching function with an improved performance by helping to overcome frequent shortcomings of hydrogels such as low mechanical strength or volume change upon temporary cross-link cleavage. Specifically, shape switching without major volume alteration is possible in porous SMHs by decoupling small volume changes of pore walls on the microscale and the macroscopic sample size. Furthermore, oligomeric rather than short aliphatic side chains as molecular switches allow stabilization of the sample volumes. Based on those structural principles and switching functionalities, SMHs have already entered into applications as soft actuators and are considered, for example, for cell manipulation in biomedicine. In the context of those applications, switching kinetics, switching forces, and reversibility of switching are aspects to be further explored.

Molecularly Stretchable Electronics for Energy and Healthcare

NASA Astrophysics Data System (ADS)

Lipomi, Darren

The term ``plastic electronics'' masks the wide range of mechanical behavior possessed by films of π-conjugated (semiconducting) small molecules and polymers. Such materials are promising for biosensors, large-area displays, low-energy lighting, and low-cost photovoltaic modules. There is also an apparent trade-off between electronic performance and mechanical compliance in films of some of the best-performing semiconducting polymers, which fracture at tensile strains not significantly greater than those at which conventional inorganic semiconductors fail. The design of intrinsically deformable electronic materials-i.e., imagine a semiconducting rubber band-would facilitate roll-to-roll production, mechanical robustness for potable applications, and conformal bonding to curved surfaces. This seminar describes my group's efforts to understand and control the structural parameters that influence the mechanical properties of π-conjugated polymers. The techniques we employ include synthetic chemistry, spectroscopy and microstructural characterization, computation from the molecular to continuum level, and electrical measurements of devices. A complex picture emerges for the interplay between molecular structure, the way the process of solidification influences the morphology, and how molecular structure and morphology combine to produce a film with a given modulus, elastic range, ductility, and toughness. We are also exploring ways to introduce other properties into organic semiconductors that are inspired by biological tissue. That is, not just elasticity and toughness, but also biodegradability and the capacity for self-repair. The seminar will also touch on our use of self-assembled metallic nanoislands on graphene for ultra-sensitive mechanical sensing using piezoresistive and ``piezoplasmonic'' mechanisms. The applications for these materials are in detecting human motion and measuring the mechanics of cardiac and musculoskeletal cells. My group is broadly interested in the intersection of soft materials and human touch for virtual and augmented reality, and I will briefly mention our work in these areas. Invited speaker #45067.

Coarse-grained simulation of molecular mechanisms of recovery in thermally activated shape-memory polymers

NASA Astrophysics Data System (ADS)

Abberton, Brendan C.; Liu, Wing Kam; Keten, Sinan

2013-12-01

Thermally actuated shape-memory polymers (SMPs) are capable of being programmed into a temporary shape and then recovering their permanent reference shape upon exposure to heat, which facilitates a phase transition that allows dramatic increase in molecular mobility. Experimental, analytical, and computational studies have established empirical relations of the thermomechanical behavior of SMPs that have been instrumental in device design. However, the underlying mechanisms of the recovery behavior and dependence on polymer microstructure remain to be fully understood for copolymer systems. This presents an opportunity for bottom-up studies through molecular modeling; however, the limited time-scales of atomistic simulations prohibit the study of key performance metrics pertaining to recovery. In order to elucidate the effects of phase fraction, recovery temperature, and deformation temperature on shape recovery, here we investigate the shape-memory behavior in a copolymer model with coarse-grained potentials using a two-phase molecular model that reproduces physical crosslinking. Our simulation protocol allows observation of upwards of 90% strain recovery in some cases, at time-scales that are on the order of the timescale of the relevant relaxation mechanism (stress relaxation in the unentangled soft-phase). Partial disintegration of the glassy phase during mechanical deformation is found to contribute to irrecoverable strain. Temperature dependence of the recovery indicates nearly full elastic recovery above the trigger temperature, which is near the glass-transition temperature of the rubbery switching matrix. We find that the trigger temperature is also directly correlated with the deformation temperature, indicating that deformation temperature influences the recovery temperatures required to obtain a given amount of shape recovery, until the plateau regions overlap above the transition region. Increasing the fraction of glassy phase results in higher strain recovery at low to intermediate temperatures, a widening of the transition region, and an eventual crossover at high temperatures. Our results corroborate experimental findings on shape-memory behavior and provide new insight into factors governing deformation recovery that can be leveraged in biomaterials design. The established computational methodology can be extended in straightforward ways to investigate the effects of monomer chemistry, low-molecular-weight solvents, physical and chemical crosslinking, different phase-separation morphologies, and more complicated mechanical deformation toward predictive modeling capabilities for stimuli-responsive polymers.

Microstructure of Amorphous and Semi-Crystalline Polymers.

DTIC Science & Technology

1981-06-07

of these materials. Further, the occurrence of nodular structures is difficult to reconcile with the results of studies of small angle neutron ...scattering and small angle neutron scattering studies of the same materials. Based on the combined results of these studies , it is suggested that the nodular...relevance here were reviewed by Flory.’ In addition to these, the results of studies using small angle neutron scattering’ and wide angle X-ray scattering

Development of Semicrystalline Morphology of Poly(L-lactic acid) During Processing of a Vascular Scaffold

NASA Astrophysics Data System (ADS)

Ailianou, Artemis

New and promising treatments for coronary heart disease are enabled by vascular scaffolds made of poly(L-lactic acid) (PLLA), as demonstrated by Abbott Vascular's bioresorbable vascular scaffold. PLLA is a semicrystalline polymer whose degree of crystallinity and crystalline microstructure depend on the thermal and deformation history during processing. In turn, the semicrystalline morphology determines scaffold strength and biodegradation time. However, spatially-resolved information about the resulting material structure (crystallinity and crystal orientation) is needed to interpret in vivo observations. The first manufacturing step of the scaffold is tube expansion in a process similar to injection blow molding. Spatial uniformity of the tube microstructure is essential for the consistent production and performance of the final scaffold. For implantation into the artery, solid-state deformation below the glass transition temperature is imposed on a laser-cut subassembly to crimp it into a small diameter. Regions of localized strain during crimping are implicated in deployment behavior. To examine the semicrystalline microstructure development of the scaffold, we employed complementary techniques of scanning electron and polarized light microscopy, wide-angle X-ray scattering, and X-ray microdiffraction. These techniques enabled us to assess the microstructure at the micro and nano length scale. The results show that the expanded tube is very uniform in the azimuthal and axial directions and that radial variations are more pronounced. The crimping step dramatically changes the microstructure of the subassembly by imposing extreme elongation and compression. Spatial information on the degree and direction of chain orientation from X-ray microdiffraction data gives insight into the mechanism by which the PLLA dissipates the stresses during crimping, without fracture. Finally, analysis of the microstructure after deployment shows that it is inherited from the crimping step and contributes to the scaffold's successful implantation in vivo.

Research on non-direct reflection columnar microstructure

NASA Astrophysics Data System (ADS)

Wu, B. Q.; Wang, X. Z.; Dong, L. H.

2015-10-01

To minimize the risk of laser accidents, especially those involving eye and skin injuries, it is crucial to pay more attention to laser safety. To control the risk of injury, depending on the laser power and wavelength, a number of required safety measures have been put forward, such as specific protection walls, and wearing safety goggles when operating lasers. The direct reflection columnar microstructure can also be used for laser safety. Based on mathematical foundations , a columnar microstructure is designed by the optical design software LightTools. Simulation showed that there is a tilt angle between the emergent and incident light, the incident light being perpendicular to the microstructure, as well as the phenomenon of no direct reflection happened. A novel testing platform was built for the columnar microstructure after it was machined. The applied testing method can measure the angle between the emergent and incident light. The method lays the condition for the further research. It is shown that the columnar microstructure with no direct reflection can be utilized in laser protection systems.

Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

PubMed

Ye, Long; Zhang, Shaoqing; Huo, Lijun; Zhang, Maojie; Hou, Jianhui

2014-05-20

As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account correlates the molecular structures of the 2D-conjugated BDT-based polymers with their photovoltaic properties. As a result, this Account can guide the molecular design of organic photovoltaic materials and the development of organic materials for other types of optoelectronic devices.

Investigations on birefringence effects in polymer optical fiber Bragg gratings

NASA Astrophysics Data System (ADS)

Hu, X.; Sáez-Rodríguez, D.; Bang, O.; Webb, D. J.; Caucheteur, C.

2014-05-01

Step-index polymer optical fiber Bragg gratings (POFBGs) and microstructured polymer optical fiber Bragg gratings (mPOFBGs) present several attractive features, especially for sensing purposes. In comparison to FBGs written in silica fibers, they are more sensitive to temperature and pressure because of the larger thermo-optic coefficient and smaller Young's modulus of polymer materials. (M)POFBGs are most often photowritten in poly(methylmethacrylate) (PMMA) materials using a continuous-wave 325 nm HeCd laser. For the first time to the best of our knowledge, we study photoinduced birefringence effects in (m)POFBGs. To achieve this, highly reflective gratings were inscribed with the phase mask technique. They were then monitored in transmission with polarized light. For this, (m)POF sections a few cm in length containing the gratings were glued to angled silica fibers. Polarization dependent loss (PDL) and differential group delay (DGD) were computed from the Jones matrix eigenanalysis using an optical vector analyser. Maximum values exceeding several dB and a few picoseconds were obtained for the PDL and DGD, respectively. The response to lateral force was finally investigated. As it induces birefringence in addition to the photo-induced one, an increase of the PDL and DGD values were noticed.

Optical studies of photoactive states in mixed organic-inorganic hybrid perovskites stabilized in polymers

NASA Astrophysics Data System (ADS)

Kardynal, Beata; Xi, Lifei; Salim, Teddy; Borghardt, Sven; Stoica, Toma; Lam, Yeng Ming

2015-03-01

Mixed organic-inorganic hybrid perovskites MAX-PbY2(X,Y =I, Br,Cl) have been demonstrated as very attractive materials for absorbers of solar cells and active layers of light emitting diodes and optically driven lasers. The bandgap of the perovskites can be tuned by mixing halogen atoms in different ratios. In this presentation we study mixed MAX-PbY2(X,Y =I, Br, Cl) particles synthesized directly in protective polymer matrices as light emitters. Both, time integrated and time resolved photoluminescence have been used to study the materials. So synthesized MAX-PbX2 are very stable when measured at room temperature and in air with radiative recombination of photogenerated carriers as the main decay path. In contrast, MAX-PbY2 with mixed halogen atoms display luminescence from sub-bandgap states which saturate at higher excitation levels. The density of these states depends on the used polymer matrix and increases upon illumination. We further compare the MAX-PbY2 synthesized in polymers and as films and show that these states are inherent to the material rather than its microstructure. This works has been supported by EU NWs4LIGHT grant.

Reducing the efficiency-stability-cost gap of organic photovoltaics with highly efficient and stable small molecule acceptor ternary solar cells

NASA Astrophysics Data System (ADS)

Baran, Derya; Ashraf, Raja Shahid; Hanifi, David A.; Abdelsamie, Maged; Gasparini, Nicola; Röhr, Jason A.; Holliday, Sarah; Wadsworth, Andrew; Lockett, Sarah; Neophytou, Marios; Emmott, Christopher J. M.; Nelson, Jenny; Brabec, Christoph J.; Amassian, Aram; Salleo, Alberto; Kirchartz, Thomas; Durrant, James R.; McCulloch, Iain

2017-03-01

Technological deployment of organic photovoltaic modules requires improvements in device light-conversion efficiency and stability while keeping material costs low. Here we demonstrate highly efficient and stable solar cells using a ternary approach, wherein two non-fullerene acceptors are combined with both a scalable and affordable donor polymer, poly(3-hexylthiophene) (P3HT), and a high-efficiency, low-bandgap polymer in a single-layer bulk-heterojunction device. The addition of a strongly absorbing small molecule acceptor into a P3HT-based non-fullerene blend increases the device efficiency up to 7.7 +/- 0.1% without any solvent additives. The improvement is assigned to changes in microstructure that reduce charge recombination and increase the photovoltage, and to improved light harvesting across the visible region. The stability of P3HT-based devices in ambient conditions is also significantly improved relative to polymer:fullerene devices. Combined with a low-bandgap donor polymer (PBDTTT-EFT, also known as PCE10), the two mixed acceptors also lead to solar cells with 11.0 +/- 0.4% efficiency and a high open-circuit voltage of 1.03 +/- 0.01 V.

Thermal aging of interfacial polymer chains in ethylene-propylene-diene terpolymer/aluminum hydroxide composites: solid-state NMR study.

PubMed

Gabrielle, Brice; Lorthioir, Cédric; Lauprêtre, Françoise

2011-11-03

The possible influence of micrometric-size filler particles on the thermo-oxidative degradation behavior of the polymer chains at polymer/filler interfaces is still an open question. In this study, a cross-linked ethylene-propylene-diene (EPDM) terpolymer filled by aluminum trihydrate (ATH) particles is investigated using (1)H solid-state NMR. The time evolution of the EPDM network microstructure under thermal aging at 80 °C is monitored as a function of the exposure time and compared to that of an unfilled EPDM network displaying a similar initial structure. While nearly no variations of the topology are observed on the neat EPDM network over 5 days at 80 °C, a significant amount of chain scission phenomena are evidenced in EPDM/ATH. A specific surface effect induced by ATH on the thermodegradative properties of the polymer chains located in their vicinity is thus pointed out. Close to the filler particles, a higher amount of chain scissions are detected, and the characteristic length scale related to these interfacial regions displaying a significant thermo-oxidation process is determined as a function of the aging time.

Determining the structure-mechanics relationships of dense microtubule networks with confocal microscopy and magnetic tweezers-based microrheology.

PubMed

Yang, Yali; Valentine, Megan T

2013-01-01

The microtubule (MT) cytoskeleton is essential in maintaining the shape, strength, and organization of cells. Its spatiotemporal organization is fundamental for numerous dynamic biological processes, and mechanical stress within the MT cytoskeleton provides an important signaling mechanism in mitosis and neural development. This raises important questions about the relationships between structure and mechanics in complex MT structures. In vitro, reconstituted cytoskeletal networks provide a minimal model of cell mechanics while also providing a testing ground for the fundamental polymer physics of stiff polymer gels. Here, we describe our development and implementation of a broad tool kit to study structure-mechanics relationships in reconstituted MT networks, including protocols for the assembly of entangled and cross-linked MT networks, fluorescence imaging, microstructure characterization, construction and calibration of magnetic tweezers devices, and mechanical data collection and analysis. In particular, we present the design and assembly of three neodymium iron boron (NdFeB)-based magnetic tweezers devices optimized for use with MT networks: (1) high-force magnetic tweezers devices that enable the application of nano-Newton forces and possible meso- to macroscale materials characterization; (2) ring-shaped NdFeB-based magnetic tweezers devices that enable oscillatory microrheology measurements; and (3) portable magnetic tweezers devices that enable direct visualization of microscale deformation in soft materials under applied force. Copyright © 2013 Elsevier Inc. All rights reserved.

Anisotropic thermal conductivity in epoxy-bonded magnetocaloric composites

NASA Astrophysics Data System (ADS)

Weise, Bruno; Sellschopp, Kai; Bierdel, Marius; Funk, Alexander; Bobeth, Manfred; Krautz, Maria; Waske, Anja

2016-09-01

Thermal management is one of the crucial issues in the development of magnetocaloric refrigeration technology for application. In order to ensure optimal exploitation of the materials "primary" properties, such as entropy change and temperature lift, thermal properties (and other "secondary" properties) play an important role. In magnetocaloric composites, which show an increased cycling stability in comparison to their bulk counterparts, thermal properties are strongly determined by the geometric arrangement of the corresponding components. In the first part of this paper, the inner structure of a polymer-bonded La(Fe, Co, Si)13-composite was studied by X-ray computed tomography. Based on this 3D data, a numerical study along all three spatial directions revealed anisotropic thermal conductivity of the composite: Due to the preparation process, the long-axis of the magnetocaloric particles is aligned along the xy plane which is why the in-plane thermal conductivity is larger than the thermal conductivity along the z-axis. Further, the study is expanded to a second aspect devoted to the influence of particle distribution and alignment within the polymer matrix. Based on an equivalent ellipsoids model to describe the inner structure of the composite, numerical simulation of the thermal conductivity in different particle arrangements and orientation distributions were performed. This paper evaluates the possibilities of microstructural design for inducing and adjusting anisotropic thermal conductivity in magnetocaloric composites.

Designing interlayers to improve the mechanical reliability of transparent conductive oxide coatings on flexible substrates

NASA Astrophysics Data System (ADS)

Kim, Eun-Hye; Yang, Chan-Woo; Park, Jin-Woo

2012-05-01

In this study, we investigate the effect of interlayers on the mechanical properties of transparent conductive oxide (TCO) on flexible polymer substrates. Indium tin oxide (ITO), which is the most widely used TCO film, and Ti, which is the most widely used adhesive interlayer, are selected as the coating and the interlayer, respectively. These films are deposited on the polymer substrates using dc-magnetron sputtering to achieve varying thicknesses. The changes in the following critical factors for film cracking and delamination are analyzed: the internal stress (σi) induced in the coatings during deposition using a white light interferometer, the crystallinity using a transmission electron microscope, and the surface roughness of ITO caused by the interlayer using an atomic force microscope. The resistances to the cracking and delamination of ITO are evaluated using a fragmentation test. Our tests and analyses reveal the important role of the interlayers, which significantly reduce the compressive σi that is induced in the ITO and increase the resistance to the buckling delamination of the ITO. However, the relaxation of σi is not beneficial to cracking because there is less compensation for the external tension as σi further decreases. Based on these results, the microstructural control is revealed as a more influential factor than σi for improving crack resistance.

Microstructure design for fast oxygen conduction

DOE PAGES

Aidhy, Dilpuneet S.; Weber, William J.

2015-11-11

Research from the last decade has shown that in designing fast oxygen conducting materials for electrochemical applications has largely shifted to microstructural features, in contrast to material-bulk. In particular, understanding oxygen energetics in heterointerface materials is currently at the forefront, where interfacial tensile strain is being considered as the key parameter in lowering oxygen migration barriers. Nanocrystalline materials with high densities of grain boundaries have also gathered interest that could possibly allow leverage over excess volume at grain boundaries, providing fast oxygen diffusion channels similar to those previously observed in metals. In addition, near-interface phase transformations and misfit dislocations aremore » other microstructural phenomenon/features that are being explored to provide faster diffusion. In this review, the current understanding on oxygen energetics, i.e., thermodynamics and kinetics, originating from these microstructural features is discussed. Moreover, our experimental observations, theoretical predictions and novel atomistic mechanisms relevant to oxygen transport are highlighted. In addition, the interaction of dopants with oxygen vacancies in the presence of these new microstructural features, and their future role in the design of future fast-ion conductors, is outlined.« less

Donor polymer design enables efficient non-fullerene organic solar cells

PubMed Central

Li, Zhengke; Jiang, Kui; Yang, Guofang; Lai, Joshua Yuk Lin; Ma, Tingxuan; Zhao, Jingbo; Ma, Wei; Yan, He

2016-01-01

To achieve efficient organic solar cells, the design of suitable donor–acceptor couples is crucially important. State-of-the-art donor polymers used in fullerene cells may not perform well when they are combined with non-fullerene acceptors, thus new donor polymers need to be developed. Here we report non-fullerene organic solar cells with efficiencies up to 10.9%, enabled by a novel donor polymer that exhibits strong temperature-dependent aggregation but with intentionally reduced polymer crystallinity due to the introduction of a less symmetric monomer unit. Our comparative study shows that an analogue polymer with a C2 symmetric monomer unit yields highly crystalline polymer films but less efficient non-fullerene cells. Based on a monomer with a mirror symmetry, our best donor polymer exhibits reduced crystallinity, yet such a polymer matches better with small molecular acceptors. This study provides important insights to the design of donor polymers for non-fullerene organic solar cells. PMID:27782112

Nanoscale Reinforced, Polymer Derived Ceramic Matrix Coatings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajendra Bordia

The goal of this project was to explore and develop a novel class of nanoscale reinforced ceramic coatings for high temperature (600-1000 C) corrosion protection of metallic components in a coal-fired environment. It was focused on developing coatings that are easy to process and low cost. The approach was to use high-yield preceramic polymers loaded with nano-size fillers. The complex interplay of the particles in the polymer, their role in controlling shrinkage and phase evolution during thermal treatment, resulting densification and microstructural evolution, mechanical properties and effectiveness as corrosion protection coatings were investigated. Fe-and Ni-based alloys currently used in coal-firedmore » environments do not possess the requisite corrosion and oxidation resistance for next generation of advanced power systems. One example of this is the power plants that use ultra supercritical steam as the working fluid. The increase in thermal efficiency of the plant and decrease in pollutant emissions are only possible by changing the properties of steam from supercritical to ultra supercritical. However, the conditions, 650 C and 34.5 MPa, are too severe and result in higher rate of corrosion due to higher metal temperatures. Coating the metallic components with ceramics that are resistant to corrosion, oxidation and erosion, is an economical and immediate solution to this problem. Good high temperature corrosion protection ceramic coatings for metallic structures must have a set of properties that are difficult to achieve using established processing techniques. The required properties include ease of coating complex shapes, low processing temperatures, thermal expansion match with metallic structures and good mechanical and chemical properties. Nanoscale reinforced composite coatings in which the matrix is derived from preceramic polymers have the potential to meet these requirements. The research was focused on developing suitable material systems and processing techniques for these coatings. In addition, we investigated the effect of microstructure on the mechanical properties and oxidation protection ability of the coatings. Coatings were developed to provide oxidation protection to both ferritic and austentic alloys and Ni-based alloys. The coatings that we developed are based on low viscosity pre-ceramic polymers. Thus they can be easily applied to any shape by using a variety of techniques including dip-coating, spray-coating and painting. The polymers are loaded with a variety of nanoparticles. The nanoparticles have two primary roles: control of the final composition and phases (and hence the properties); and control of the shrinkage during thermal decomposition of the polymer. Thus the selection of the nanoparticles was the most critical aspect of this project. Based on the results of the processing studies, the performance of selected coatings in oxidizing conditions (both static and cyclic) was investigated.« less

Independent effects of the chemical and microstructural surface properties of polymer/ceramic composites on proliferation and osteogenic differentiation of human MSCs.

PubMed

Sun, Lanying; Danoux, Charlène B; Wang, Qibao; Pereira, Daniel; Barata, David; Zhang, Jingwei; LaPointe, Vanessa; Truckenmüller, Roman; Bao, Chongyun; Xu, Xin; Habibovic, Pamela

2016-09-15

Within the general aim of finding affordable and sustainable regenerative solutions for damaged and diseased tissues and organs, significant efforts have been invested in developing synthetic alternatives to natural bone grafts, such as autografts. Calcium phosphate (CaP) ceramics are among widely used synthetic bone graft substitutes, but their mechanical properties and bone regenerative capacity are still outperformed by their natural counterparts. In order to improve the existing synthetic bone graft substitutes, it is imperative to understand the effects of their individual properties on a biological response, and to find a way to combine the desired properties into new, improved functional biomaterials. To this end, we studied the independent effects of the chemical composition and surface microstructure of a poly(lactic acid)/hydroxyapatite (PLA/HA) composite material on the proliferation and osteogenic differentiation of clinically relevant bone marrow-derived human mesenchymal stromal cells (hMSCs). While the molecular weight of the polymer and presence/absence of the ceramic phase were used as the chemical variables, a soft embossing technique was used to pattern the surfaces of all materials with either pits or pillars with identical microscale dimensions. The results indicated that, while cell morphology was affected by both the presence and availability of HA and by the surface microstructure, the effect of the latter parameter on cell proliferation was negligible. The osteogenic differentiation of hMSCs, and in particular the expression of bone morphogenetic protein 2 (BMP-2) and osteopontin (OP) were significantly enhanced when cells were cultured on the composite based on low-molecular-weight PLA, as compared to the high-molecular-weight PLA-based composite and the two pure polymers. The OP expression on the low-molecular-weight PLA-based composite was further enhanced when the surface was patterned with pits. Taken together, within this experimental set up, the individual effect of the chemistry, and in particular of the presence of CaP, was more pronounced than the individual effect of the surface microstructure, although their combined effects were, in some cases, synergistic. The approach presented here opens new routes to study the interactions of biomaterials with the biological environment in greater depths, which can serve as a starting point for developing biomaterials with improved bioactivity. The aim of the this study was to obtain insight into independent effects of the chemical composition and surface microstructure of a poly(lactic acid)/hydroxyapatite (PLA/HA) composite material on the morphology, proliferation and osteogenic differentiation of clinically relevant bone marrow-derived human mesenchymal stromal cells (hMSCs). While the need for synthetic alternatives for natural bone in bone regenerative strategies is rapidly increasing, the clinical performance of synthetic biomaterials needs to be further improved. To do this successfully, we believe that a better understanding of the relationship between a property of a material and a biological response is imperative. This study is a step forward in this direction, and we are therefore convinced that it will be of interest to the readers of Acta Biomaterialia. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Optical fabrication of large area photonic microstructures by spliced lens

NASA Astrophysics Data System (ADS)

Jin, Wentao; Song, Meng; Zhang, Xuehua; Yin, Li; Li, Hong; Li, Lin

2018-05-01

We experimentally demonstrate a convenient approach to fabricate large area photorefractive photonic microstructures by a spliced lens device. Large area two-dimensional photonic microstructures are optically induced inside an iron-doped lithium niobate crystal. The experimental setups of our method are relatively compact and stable without complex alignment devices. It can be operated in almost any optical laboratories. We analyze the induced triangular lattice microstructures by plane wave guiding, far-field diffraction pattern imaging and Brillouin-zone spectroscopy. By designing the spliced lens appropriately, the method can be easily extended to fabricate other complex large area photonic microstructures, such as quasicrystal microstructures. Induced photonic microstructures can be fixed or erased and re-recorded in the photorefractive crystal.

Printing of microstructure strain sensor for structural health monitoring

NASA Astrophysics Data System (ADS)

Le, Minh Quyen; Ganet, Florent; Audigier, David; Capsal, Jean-Fabien; Cottinet, Pierre-Jean

2017-05-01

Recent advances in microelectronics and materials should allow the development of integrated sensors with transduction properties compatible with being printed directly onto a 3D substrate, especially metallic and polymer substrates. Inorganic and organic electronic materials in microstructured and nanostructured forms, intimately integrated in ink, offer particularly attractive characteristics, with realistic pathways to sophisticated embodiments. Here, we report on these strategies and demonstrate the potential of 3D-printed microelectronics based on a structural health monitoring (SHM) application for the precision weapon systems. We show that our printed sensors can be employed in non-invasive, high-fidelity and continuous strain monitoring of handguns, making it possible to implement printed sensors on a 3D substrate in either SHM or remote diagnostics. We propose routes to commercialization and novel device opportunities and highlight the remaining challenges for research.

Development of a High Performance Acousto-ultrasonic Scan System

NASA Technical Reports Server (NTRS)

Roth, D. J.; Martin, R. E.; Harmon, L. M.; Gyekenyesi, A. L.; Kautz, H. E.

2002-01-01

Acousto-ultrasonic (AU) interrogation is a single-sided nondestructive evaluation (NDE) technique employing separated sending and receiving transducers. It is used for assessing the microstructural condition/distributed damage state of the material between the transducers. AU is complementary to more traditional NDE methods such as ultrasonic c-scan, x-ray radiography, and thermographic inspection that tend to be used primarily for discrete flaw detection. Through its history, AU has been used to inspect polymer matrix composite, metal matrix composite, ceramic matrix composite, and even monolithic metallic materials. The development of a high-performance automated AU scan system for characterizing within-sample microstructural and property homogeneity is currently in a prototype stage at NASA. In this paper, a review of essential AU technology is given. Additionally, the basic hardware and software configuration, and preliminary results with the system, are described.

Fundamental molecular design for precise control of thermoresponsiveness of organic polymers by using ternary systems.

PubMed

Amemori, Shogo; Kokado, Kenta; Sada, Kazuki

2012-05-23

The de novo design of thermosensitive polymers in solution has been achieved by using the addition of small organic molecules (or "effectors"). Hydrogen bonding as an attractive polymer-polymer or polymer-effector interaction substantially dominates the responsivity, causing facile switching between LCST-type and UCST-type phase transitions, control of the transition temperature, and further coincidence of the two transitions. Small molecules having a high affinity for the polymer induce UCST-type phase behavior, whereas those having a low affinity for the polymer showed LCST-type phase behavior.

Liquid water breakthrough location distances on a gas diffusion layer of polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Yu, Junliang; Froning, Dieter; Reimer, Uwe; Lehnert, Werner

2018-06-01

The lattice Boltzmann method is adopted to simulate the three dimensional dynamic process of liquid water breaking through the gas diffusion layer (GDL) in the polymer electrolyte membrane fuel cell. 22 micro-structures of Toray GDL are built based on a stochastic geometry model. It is found that more than one breakthrough locations are formed randomly on the GDL surface. Breakthrough location distance (BLD) are analyzed statistically in two ways. The distribution is evaluated statistically by the Lilliefors test. It is concluded that the BLD can be described by the normal distribution with certain statistic characteristics. Information of the shortest neighbor breakthrough location distance can be the input modeling setups on the cell-scale simulations in the field of fuel cell simulation.

Positron lifetime spectroscopy in thin polymer coatings

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Eftekhari, Abe; Sprinkle, Danny R.

1990-01-01

Polymer coatings are finding increasing applications in aerospace industry. The effectiveness of coatings depends strongly on their microstructure and adhesion to the substrates. Currently, there is no technique for adequately monitoring the quality of the coatings. We adapted positron lifetime spectroscopy for the investigation of thin coatings. Results of measurements on 0.001-in-thick polyurethane coatings on aluminum and steel substrates and thicker (0.080-in.) self-standing polyurethane discs were compared. In all cases, we find positron lifetime groups centered around 560 ps, corresponding to the presence of 0.9 A exp 3 free volume cells. However, the number of free volume cells in thin coatings is larger, suggesting that the morphology of thin coatings is different from that of bulk polyurethane. These results and their structural implications are discussed.

Laser absorption of carbon fiber reinforced polymer with randomly distributed carbon fibers

NASA Astrophysics Data System (ADS)

Hu, Jun; Xu, Hebing; Li, Chao

2018-03-01

Laser processing of carbon fiber reinforced polymer (CFRP) is a non-traditional machining method which has many prospective applications. The laser absorption characteristics of CFRP are analyzed in this paper. A ray tracing model describing the interaction of the laser spot with CFRP is established. The material model contains randomly distributed carbon fibers which are generated using an improved carbon fiber placement method. It was found that CFRP has good laser absorption due to multiple reflections of the light rays in the material’s microstructure. The randomly distributed carbon fibers make the absorptivity of the light rays change randomly in the laser spot. Meanwhile, the average absorptivity fluctuation is obvious during movement of the laser. The experimental measurements agree well with the values predicted by the ray tracing model.

Cross Section High Resolution Imaging of Polymer-Based Materials

NASA Astrophysics Data System (ADS)

Delaportas, D.; Aden, P.; Muckle, C.; Yeates, S.; Treutlein, R.; Haq, S.; Alexandrou, I.

This paper describes a methodology for preparing cross sections of organic layers suitable for transmission electron microscopy (TEM) at high resolution. Our principal aim is to prepare samples that are tough enough to allow the slicing into sub-150 nm sections. We also need strong contrast at the organic layer area to make it identifiable during TEM. Our approach is to deposit organic layers on flexible substrates and prepare thin cross sections using ultra-microtomy. We sandwich the organic layer between two metal thin films in order to isolate it and improve contrast. Our methodology is used to study the microstructure of polymer/nanotube composites, allowing us to accurately measure the organic layer thickness, determine nanotube dispersion and assess the effect of nanotube clustering on film structural stability.

Periodic nanostructures from self assembled wedge-type block-copolymers

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R.; Grubbs, Robert H.; Weitekamp, Raymond; Miyake, Garret M.; Piunova, Victoria; Daeffler, Christopher Scot

2015-06-02

The invention provides a class of wedge-type block copolymers having a plurality of chemically different blocks, at least a portion of which incorporates a wedge group-containing block providing useful properties. For example, use of one or more wedge group-containing blocks in some block copolymers of the invention significantly inhibits chain entanglement and, thus, the present block copolymers materials provide a class of polymer materials capable of efficient molecular self-assembly to generate a range of structures, such as periodic nanostructures and microstructures. Materials of the present invention include copolymers having one or more wedge group-containing blocks, and optionally for some applications copolymers also incorporating one or more polymer side group-containing blocks. The present invention also provides useful methods of making and using wedge-type block copolymers.

Tunable thiol-epoxy shape memory polymer foams

NASA Astrophysics Data System (ADS)

Ellson, Gregory; Di Prima, Matthew; Ware, Taylor; Tang, Xiling; Voit, Walter

2015-05-01

Shape memory polymers (SMPs) are uniquely suited to a number of applications due to their shape storage and recovery abilities and the wide range of available chemistries. However, many of the desired performance properties are tied to the polymer chemistry which can make optimization difficult. The use of foaming techniques is one way to tune mechanical response of an SMP without changing the polymer chemistry. In this work, a novel thiol-epoxy SMP was foamed using glass microspheres (40 and 50% by volume Q-Cel 6019), using expandable polymer microspheres (1% 930 DU 120), and by a chemical blowing agent (1% XOP-341). Each approach created SMP foam with a differing density and microstructure from the others. Thermal and thermomechanical analysis was performed to observe the behavioral difference between the foaming techniques and to confirm that the glass transition (Tg) was relatively unchanged near 50 °C while the glassy modulus varied from 19.1 to 345 MPa and the rubbery modulus varied from 0.04 to 2.2 MPa. The compressive behavior of the foams was characterized through static compression testing at different temperatures, and cyclic compression testing at Tg. Constrained shape recovery testing showed a range of peak recovery stress from 5 MPa for the syntactic Q-Cel foams to ˜0.1 MPa for the chemically blown XOP-341 foam. These results showed that multiple foaming approaches can be used with a novel SMP to vary the mechanical response independent of Tg and polymer chemistry.

Preparation and Performance of Plasma/Polymer Composite Coatings on Magnesium Alloy

NASA Astrophysics Data System (ADS)

Bakhsheshi-Rad, H. R.; Hamzah, E.; Bagheriyan, S.; Daroonparvar, M.; Kasiri-Asgarani, M.; Shah, A. M.; Medraj, M.

2016-09-01

A triplex plasma (NiCoCrAlHfYSi/Al2O3·13%TiO2)/polycaprolactone composite coating was successfully deposited on a Mg-1.2Ca alloy by a combination of atmospheric plasma spraying and dip-coating techniques. The NiCoCrAlHfYSi (MCrAlHYS) coating, as the first layer, contained a large number of voids, globular porosities, and micro-cracks with a thickness of 40-50 μm, while the Al2O3·13%TiO2 coating, as the second layer, presented a unique bimodal microstructure with a thickness of 70-80 μm. The top layer was a hydrophobic polymer, which effectively sealed the porosities of plasma layers. The results of micro-hardness and bonding strength tests showed that the plasma coating presented excellent hardness (870 HV) and good bonding strength (14.8 MPa). However, the plasma/polymer coatings interface exhibited low bonding strength (8.6 MPa). The polymer coating formed thick layer (100-110 μm) that homogeneously covered the surface of the plasma layers. Contact angle measurement showed that polymer coating over plasma layers significantly decreased surface wettability. The corrosion current density ( i corr) of an uncoated sample (262.7 µA/cm2) decreased to 76.9 µA/cm2 after plasma coatings were applied. However, it was found that the i corr decreased significantly to 0.002 µA/cm2 after polymer sealing of the porous plasma layers.

Three-Dimensional Multiscale, Multistable, and Geometrically Diverse Microstructures with Tunable Vibrational Dynamics Assembled by Compressive Buckling.

PubMed

Ning, Xin; Wang, Heling; Yu, Xinge; Soares, Julio A N T; Yan, Zheng; Nan, Kewang; Velarde, Gabriel; Xue, Yeguang; Sun, Rujie; Dong, Qiyi; Luan, Haiwen; Lee, Chan Mi; Chempakasseril, Aditya; Han, Mengdi; Wang, Yiqi; Li, Luming; Huang, Yonggang; Zhang, Yihui; Rogers, John

2017-04-11

Microelectromechanical systems remain an area of significant interest in fundamental and applied research due to their wide ranging applications. Most device designs, however, are largely two-dimensional and constrained to only a few simple geometries. Achieving tunable resonant frequencies or broad operational bandwidths requires complex components and/or fabrication processes. The work presented here reports unusual classes of three-dimensional (3D) micromechanical systems in the form of vibratory platforms assembled by controlled compressive buckling. Such 3D structures can be fabricated across a broad range of length scales and from various materials, including soft polymers, monocrystalline silicon, and their composites, resulting in a wide scope of achievable resonant frequencies and mechanical behaviors. Platforms designed with multistable mechanical responses and vibrationally de-coupled constituent elements offer improved bandwidth and frequency tunability. Furthermore, the resonant frequencies can be controlled through deformations of an underlying elastomeric substrate. Systematic experimental and computational studies include structures with diverse geometries, ranging from tables, cages, rings, ring-crosses, ring-disks, two-floor ribbons, flowers, umbrellas, triple-cantilever platforms, and asymmetric circular helices, to multilayer constructions. These ideas form the foundations for engineering designs that complement those supported by conventional, microelectromechanical systems, with capabilities that could be useful in systems for biosensing, energy harvesting and others.

Functional and Multifunctional Polymers: Materials for Smart Structures

NASA Technical Reports Server (NTRS)

Arnold, S.; Pratt, L. M.; Li, J.; Wuagaman, M.; Khan, I. M.

1996-01-01

The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three examples of multifunctional polymers developed in our labs will be reported. The first class of multifunctional polymers are the microphase separated mixed (ionic and electronic) conducting or MIEC block copolymers. The second class being developed in our labs are the biocompatible conductive materials and the conductive fluids. The final class may be considered microwave active smart polymers.

Microstructure and Mechanical Properties of Additively Manufactured Parts with Staircase Feature

NASA Astrophysics Data System (ADS)

Keya, Tahmina

This thesis focuses on a part with staircase feature that is made of Inconel 718 and fabricated by SLM process. The objective of the study was to observe build height effect on the microstructure and mechanical properties of the part. Due to the nature of SLM, there is possibility of different microstructure and mechanical properties in different locations depending on the design of the part. The objective was to compare microstructure and mechanical properties from different location and four comparison groups were considered: 1. Effect of thermal cycle; 2. External and internal surfaces; 3. Build height effect and 4. Bottom surfaces. To achieve the goals of this research, standard metallurgical procedure has been performed to prepare samples. Etching was done to reveal the microstructure of SLM processed Inconel 718 parts. Young's modulus and hardness were measured using nanoindentation technique. FEM analysis was performed to simulate nanoindentation. The conclusions drawn from this research are: 1. The microstructure of front and side surface of SLM processed Inconel 718 consists of arc shaped cut ends of melt pools with intermetallic phase at the border of the melt pool; 2. On top surface, melted tracks and scanning patterns can be observed and the average width of melted tracks is 100-150 microm; 3. The microstructure looks similar at different build height; 4. Microstructure on the top of a stair is more defined and organized than the internal surface; 5. The mechanical properties are highest at the bottom. OM images revealed slight difference in microstructure in terms of build height for this specific part, but mechanical properties seem to be vary noticeably. This is something to be kept in mind while designing or determining build orientation. External and internal surfaces of a stair at the same height showed difference in both microstructure and mechanical properties. To minimize that effect and to make it more uniform, gradual elevation can be considered when suitable as far as design modification is concerned. Above all, this study reveals important information about the pattern of microstructure, thus heat transfer mechanism inside a part which is useful to understand the SLM process.

Microstructured polymer films by X-ray lithographic exposure and grafting

NASA Astrophysics Data System (ADS)

Gürsel, Selmiye A.; Padeste, Celestino; Solak, Harun H.; Scherer, Günther G.

2005-07-01

Recently we reported on a new technique to generate micro- and nanostructured polymer materials by the combination of selective irradiation of polymer substrates with X-rays and subsequent grafting of a second polymer. Here we focus on the spatially defined grafting throughout the thickness of poly(ethylene-alt-tetrafluoroethylene) (ETFE) and poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) films using X-ray irradiation through a metal mask, followed by grafting with styrene. Calculations of the transmission of X-rays through the polymer as a function of the wavelength have revealed that energy deposition within the substrate material, which should control the density of created radicals, can be selected in a wide range. Depending on the used wavelength the radicals are created either near the surface or in the bulk of the sample. First experiments demonstrated spatially defined grafting through a 100 μm thick ETFE film and 25 μm thick FEP film. The achieved graft level depends on the irradiation dose as well as on the grafting parameters such as concentration, temperature and time. The precision of structure definition within the film depends on the properties of the X-ray source, the metal mask and the grafting process. The presented process allows controlled grafting through fluoropolymer films with micrometer resolution and local modification of the properties of the films, such as ion conductivity, diffusion of specific molecules or optical properties.

Synthesis, Characterisation and 3D micro-structuring via 2-Photon Polymerisation of Poly(glycerol sebacate)-Methacrylate – an Elastomeric Degradable Polymer

NASA Astrophysics Data System (ADS)

Pashneh-Tala, Samand; Owen, Robert; Bahmaee, Hossein; Rekštytė, Sima; Malinauskas, Mangirdas; Claeyssens, Frederik

2018-05-01

Poly(glycerol sebacate) (PGS) has been utilised in numerous biomaterial applications over recent years. This elastomeric and rapidly degradable polymer is cytocompatible and suited to various applications in soft tissue engineering and drug delivery. Although PGS is simple to synthesise as an insoluble prepolymer, it requires the application of high temperatures for extended periods of time to produce an insoluble matrix. This places limitations on the processing capabilities of PGS and its possible applications. Here, we present a photocurable form of PGS with improved processing capabilities: PGS-methacrylate (PGS-M). By methacrylating the secondary hydroxyl groups of the glycerol units in the PGS prepolymer chains, the material was rendered photocurable and, in combination with a photoinitiator, crosslinked rapidly on exposure to UV light at ambient temperatures. The polymer's molecular weight and the degree of methacrylation could be controlled independently and the mechanical properties of the crosslinked material tailored. The polymer also displayed rapid degradation under physiological conditions and cytocompatibility with various primary cell types. As a demonstration of the processing capabilities of PGS-M, µm scale 3D scaffold structures were fabricated using 2-photon polymerisation and used for 3D cell culture. The tunable properties of PGS-M coupled with its enhanced processing capabilities make the polymer an attractive potential biomaterial for various future applications.

Tailored Buckling Microlattices as Reusable Light-Weight Shock Absorbers.

PubMed

Frenzel, Tobias; Findeisen, Claudio; Kadic, Muamer; Gumbsch, Peter; Wegener, Martin

2016-07-01

Structures and materials absorbing mechanical (shock) energy commonly exploit either viscoelasticity or destructive modifications. Based on a class of uniaxial light-weight geometrically nonlinear mechanical microlattices and using buckling of inner elements, either a sequence of snap-ins followed by irreversible hysteretic - yet repeatable - self-recovery or multistability is achieved, enabling programmable behavior. Proof-of-principle experiments on three-dimensional polymer microstructures are presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical Behavior and Fatigue Studies of Rubber Components in Army Tracked Vehicles

DTIC Science & Technology

2010-08-13

strategy moved to glassy polymers (Bouvard et al., 2010) – Current efforts to apply ISV modeling strategy to elastomers • Fatigue approach – Researchers...metals at CAVS – Researchers have typically only investigated long crack for elastomers (Mars and Fatemi, 2003; Busfield et al., 2002; Chou et al...2007) – Current efforts are to add MSC/PSC, INC to fatigue modeling of elastomers and incorporate microstructure 13 August 2010 2 Overview 8/13/2010 3

Numerical study of elastic turbulence in a 3D curvilinear micro-channel

NASA Astrophysics Data System (ADS)

Zhang, Hongna; Kunugi, Tomoaki; Li, Fengchen

2012-11-01

Elastic turbulence is an intriguing phenomenon of viscoelastic fluid flow, and dominated by the strong nonlinear elasticity due to the existence of flexible microstructures. It implies the possibility to generate a turbulent state (so-called an elastic turbulence) in the micro-scale devices by introducing the viscoelastic fluids, which could significantly enhance the mixing efficiency therein. Several experiments have been carried out to study its characteristics and underlying physics. However, the difficulty in measuring the flow information and behaviors of the microstructures, especially in the cross section normal to the mean flow direction, limits our current understanding and controlling. In the present study, the nondimensionalization method in which the characteristic velocity is defined as the ratio of the solution viscosity to the width of the channel was adopted to simulate the elastic turbulence in the micro-scale devices. And the elastic turbulent flow was obtained numerically in the 3D curvilinear micro-channel. Therein, the characteristics of the velocity field and polymer's behavior are discussed. Moreover, the energy transfer between the kinetic energy and the polymer's elastic energy is also investigated to understand its physical mechanism. Supported by the Japan Society for the Promotion of Science research fellowship and the Ministry of Education, Culture, Sports, Science and Technology via `Energy Science in the Age of Global Warming' of Global Center of Excellence (G-COE) program (J-051).

Image-Based Macro-Micro Finite Element Models of a Canine Femur with Implant Design Implications

NASA Astrophysics Data System (ADS)

Ghosh, Somnath; Krishnan, Ganapathi; Dyce, Jonathan

2006-06-01

In this paper, a comprehensive model of a bone-cement-implant assembly is developed for a canine cemented femoral prosthesis system. Various steps in this development entail profiling the canine femur contours by computed tomography (CT) scanning, computer aided design (CAD) reconstruction of the canine femur from CT images, CAD modeling of the implant from implant blue prints and CAD modeling of the interface cement. Finite element analysis of the macroscopic assembly is conducted for stress analysis in individual components of the system, accounting for variation in density and material properties in the porous bone material. A sensitivity analysis is conducted with the macroscopic model to investigate the effect of implant design variables on the stress distribution in the assembly. Subsequently, rigorous microstructural analysis of the bone incorporating the morphological intricacies is conducted. Various steps in this development include acquisition of the bone microstructural data from histological serial sectioning, stacking of sections to obtain 3D renderings of void distributions, microstructural characterization and determination of properties and, finally, microstructural stress analysis using a 3D Voronoi cell finite element method. Generation of the simulated microstructure and analysis by the 3D Voronoi cell finite element model provides a new way of modeling complex microstructures and correlating to morphological characteristics. An inverse calculation of the material parameters of bone by combining macroscopic experiments with microstructural characterization and analysis provides a new approach to evaluating properties without having to do experiments at this scale. Finally, the microstructural stresses in the femur are computed using the 3D VCFEM to study the stress distribution at the scale of the bone porosity. Significant difference is observed between the macroscopic stresses and the peak microscopic stresses at different locations.

Interpreting Neutron Reflectivity Profiles of Diblock Copolymer Nanocomposite Thin Films Using Hybrid Particle-Field Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahalik, Jyoti P.; Dugger, Jason W.; Sides, Scott W.

Mixtures of block copolymers and nanoparticles (block copolymer nanocomposites) are known to microphase separate into a plethora of microstructures, depending on the composition, length scale and nature of interactions among its different constituents. Theoretical and experimental works on this class of nanocomposites have already high-lighted intricate relations among chemical details of the polymers, nanoparticles, and various microstructures. Confining these nanocomposites in thin films yields an even larger array of structures, which are not normally observed in the bulk. In contrast to the bulk, exploring various microstructures in thin films by the experimental route remains a challenging task. Here in thismore » work, we construct a model for the thin films of lamellar forming diblock copolymers containing spherical nanoparticles based on a hybrid particle-field approach. The model is benchmarked by comparison with the depth profiles obtained from the neutron reflectivity experiments for symmetric poly(deuterated styrene-b-n butyl methacrylate) copolymers blended with spherical magnetite nanoparticles covered with hydrogenated poly(styrene) corona. We show that the model based on a hybrid particle-field approach provides details of the underlying microphase separation in the presence of the nanoparticles through a direct comparison to the neutron reflectivity data. This work benchmarks the application of the hybrid particle-field model to extract the interaction parameters for exploring different microstructures in thin films containing block copolymers and nanocomposites.« less