Materials Knowledge Systems in Python - A Data Science Framework for Accelerated Development of Hierarchical Materials

PubMed Central

Brough, David B; Wheeler, Daniel; Kalidindi, Surya R.

2017-01-01

There is a critical need for customized analytics that take into account the stochastic nature of the internal structure of materials at multiple length scales in order to extract relevant and transferable knowledge. Data driven Process-Structure-Property (PSP) linkages provide systemic, modular and hierarchical framework for community driven curation of materials knowledge, and its transference to design and manufacturing experts. The Materials Knowledge Systems in Python project (PyMKS) is the first open source materials data science framework that can be used to create high value PSP linkages for hierarchical materials that can be leveraged by experts in materials science and engineering, manufacturing, machine learning and data science communities. This paper describes the main functions available from this repository, along with illustrations of how these can be accessed, utilized, and potentially further refined by the broader community of researchers. PMID:28690971

Hierarchical porous graphene/polyaniline composite film with superior rate performance for flexible supercapacitors.

PubMed

Meng, Yuena; Wang, Kai; Zhang, Yajie; Wei, Zhixiang

2013-12-23

A highly flexible graphene free-standing film with hierarchical structure is prepared by a facile template method. With a porous structure, the film can be easily bent and cut, and forms a composite with another material as a scaffold. The 3D graphene film exhibits excellent rate capability and its capacitance is further improved by forming a composite with polyaniline nanowire arrays. The flexible hierarchical composite proves to be an excellent electrode material for flexible supercapacitors. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of porous hierarchical polymer/ceramic composites by electron irradiation of organic/inorganic polymers: route to a highly durable, large-area superhydrophobic coating.

PubMed

Lee, Eun Je; Kim, Jae Joon; Cho, Sung Oh

2010-03-02

Polymer/ceramic composite films with micro- and nanocombined hierarchical structures are fabricated by electron irradiation of poly(methyl methacrylate) (PMMA) microspheres/silicone grease. Electron irradiation induces volume contraction of PMMA microspheres and simultaneously transforms silicone grease into a ceramic material of silicon oxycarbide with many nanobumps. As a result, highly porous structures that consist of micrometer-sized pores and microparticles decorated with nanobumps are created. The fabricated films with the porous hierarchical structure exhibit good superhydrophobicity with excellent self-cleaning and antiadhesion properties after surface treatment with fluorosilane. In addition, the porous hierarchical structures are covered with silicon oxycarbide, and thus the superhydrophobic coatings have high hardness and strong adhesion to the substrate. The presented technique provides a straightforward route to producing large-area, mechanically robust superhydrophobic films on various substrate materials.

Universal Method for Creating Hierarchical Wrinkles on Thin-Film Surfaces.

PubMed

Jung, Woo-Bin; Cho, Kyeong Min; Lee, Won-Kyu; Odom, Teri W; Jung, Hee-Tae

2018-01-10

One of the most interesting topics in physical science and materials science is the creation of complex wrinkled structures on thin-film surfaces because of their several advantages of high surface area, localized strain, and stress tolerance. In this study, a significant step was taken toward solving limitations imposed by the fabrication of previous artificial wrinkles. A universal method for preparing hierarchical three-dimensional wrinkle structures of thin films on a multiple scale (e.g., nanometers to micrometers) by sequential wrinkling with different skin layers was developed. Notably, this method was not limited to specific materials, and it was applicable to fabricating hierarchical wrinkles on all of the thin-film surfaces tested thus far, including those of metals, two-dimensional and one-dimensional materials, and polymers. The hierarchical wrinkles with multiscale structures were prepared by sequential wrinkling, in which a sacrificial layer was used as the additional skin layer between sequences. For example, a hierarchical MoS 2 wrinkle exhibited highly enhanced catalytic behavior because of the superaerophobicity and effective surface area, which are related to topological effects. As the developed method can be adopted to a majority of thin films, it is thought to be a universal method for enhancing the physical properties of various materials.

Graphene--nanotube--iron hierarchical nanostructure as lithium ion battery anode.

PubMed

Lee, Si-Hwa; Sridhar, Vadahanambi; Jung, Jung-Hwan; Karthikeyan, Kaliyappan; Lee, Yun-Sung; Mukherjee, Rahul; Koratkar, Nikhil; Oh, Il-Kwon

2013-05-28

In this study, we report a novel route via microwave irradiation to synthesize a bio-inspired hierarchical graphene--nanotube--iron three-dimensional nanostructure as an anode material in lithium-ion batteries. The nanostructure comprises vertically aligned carbon nanotubes grown directly on graphene sheets along with shorter branches of carbon nanotubes stemming out from both the graphene sheets and the vertically aligned carbon nanotubes. This bio-inspired hierarchical structure provides a three-dimensional conductive network for efficient charge-transfer and prevents the agglomeration and restacking of the graphene sheets enabling Li-ions to have greater access to the electrode material. In addition, functional iron-oxide nanoparticles decorated within the three-dimensional hierarchical structure provides outstanding lithium storage characteristics, resulting in very high specific capacities. The anode material delivers a reversible capacity of ~1024 mA · h · g(-1) even after prolonged cycling along with a Coulombic efficiency in excess of 99%, which reflects the ability of the hierarchical network to prevent agglomeration of the iron-oxide nanoparticles.

Hierarchical Cu4V2.15O9.38 micro-/nanostructures: a lithium intercalating electrode material

NASA Astrophysics Data System (ADS)

Zhou, Liang; Cui, Wangjun; Wu, Jiamin; Zhao, Qingfei; Li, Hexing; Xia, Yongyao; Wang, Yunhua; Yu, Chengzhong

2011-03-01

Hierarchical Cu4V2.15O9.38 micro-/nanostructures have been prepared by a facile ``forced hydrolysis'' method, from an aqueous peroxovanadate and cupric nitrate solution in the presence of urea. The hierarchical architectures with diameters of 10-20 µm are assembled from flexible nanosheets and rigid nanoplates with widths of 2-4 µm and lengths of 5-10 µm in a radiative way. The preliminary electrochemical properties of Cu4V2.15O9.38 have been investigated for the first time and correlated with its structure. This material delivers a large discharge capacity of 471 mA h g-1 above 1.5 V, thus making it an interesting electrode material for primary lithium ion batteries used in implantable cardioverter defibrillators.Hierarchical Cu4V2.15O9.38 micro-/nanostructures have been prepared by a facile ``forced hydrolysis'' method, from an aqueous peroxovanadate and cupric nitrate solution in the presence of urea. The hierarchical architectures with diameters of 10-20 µm are assembled from flexible nanosheets and rigid nanoplates with widths of 2-4 µm and lengths of 5-10 µm in a radiative way. The preliminary electrochemical properties of Cu4V2.15O9.38 have been investigated for the first time and correlated with its structure. This material delivers a large discharge capacity of 471 mA h g-1 above 1.5 V, thus making it an interesting electrode material for primary lithium ion batteries used in implantable cardioverter defibrillators. Electronic supplementary information (ESI) available: SEM images of hierarchical Cu4V2.15O9.38, CV curves of the electrode and discharge profiles of the cell made from Cu4V2.15O9.38 hierarchical structures, XRD pattern and SEM images of layered vanadium oxide hydrate, structure model of Cu4V2.15O9.38. See DOI: 10.1039/c0nr00657b

TiO2 nanowire-templated hierarchical nanowire network as water-repelling coating

NASA Astrophysics Data System (ADS)

Hang, Tian; Chen, Hui-Jiuan; Xiao, Shuai; Yang, Chengduan; Chen, Meiwan; Tao, Jun; Shieh, Han-ping; Yang, Bo-ru; Liu, Chuan; Xie, Xi

2017-12-01

Extraordinary water-repelling properties of superhydrophobic surfaces make them novel candidates for a great variety of potential applications. A general approach to achieve superhydrophobicity requires low-energy coating on the surface and roughness on nano- and micrometre scale. However, typical construction of superhydrophobic surfaces with micro-nano structure through top-down fabrication is restricted by sophisticated fabrication techniques and limited choices of substrate materials. Micro-nanoscale topographies templated by conventional microparticles through surface coating may produce large variations in roughness and uncontrollable defects, resulting in poorly controlled surface morphology and wettability. In this work, micro-nanoscale hierarchical nanowire network was fabricated to construct self-cleaning coating using one-dimensional TiO2 nanowires as microscale templates. Hierarchical structure with homogeneous morphology was achieved by branching ZnO nanowires on the TiO2 nanowire backbones through hydrothermal reaction. The hierarchical nanowire network displayed homogeneous micro/nano-topography, in contrast to hierarchical structure templated by traditional microparticles. This hierarchical nanowire network film exhibited high repellency to both water and cell culture medium after functionalization with fluorinated organic molecules. The hierarchical structure templated by TiO2 nanowire coating significantly increased the surface superhydrophobicity compared to vertical ZnO nanowires with nanotopography alone. Our results demonstrated a promising strategy of using nanowires as microscale templates for the rational design of hierarchical coatings with desired superhydrophobicity that can also be applied to various substrate materials.

TiO2 nanowire-templated hierarchical nanowire network as water-repelling coating

PubMed Central

Hang, Tian; Chen, Hui-Jiuan; Xiao, Shuai; Yang, Chengduan; Chen, Meiwan; Tao, Jun; Shieh, Han-ping; Yang, Bo-ru; Liu, Chuan

2017-01-01

Extraordinary water-repelling properties of superhydrophobic surfaces make them novel candidates for a great variety of potential applications. A general approach to achieve superhydrophobicity requires low-energy coating on the surface and roughness on nano- and micrometre scale. However, typical construction of superhydrophobic surfaces with micro-nano structure through top-down fabrication is restricted by sophisticated fabrication techniques and limited choices of substrate materials. Micro-nanoscale topographies templated by conventional microparticles through surface coating may produce large variations in roughness and uncontrollable defects, resulting in poorly controlled surface morphology and wettability. In this work, micro-nanoscale hierarchical nanowire network was fabricated to construct self-cleaning coating using one-dimensional TiO2 nanowires as microscale templates. Hierarchical structure with homogeneous morphology was achieved by branching ZnO nanowires on the TiO2 nanowire backbones through hydrothermal reaction. The hierarchical nanowire network displayed homogeneous micro/nano-topography, in contrast to hierarchical structure templated by traditional microparticles. This hierarchical nanowire network film exhibited high repellency to both water and cell culture medium after functionalization with fluorinated organic molecules. The hierarchical structure templated by TiO2 nanowire coating significantly increased the surface superhydrophobicity compared to vertical ZnO nanowires with nanotopography alone. Our results demonstrated a promising strategy of using nanowires as microscale templates for the rational design of hierarchical coatings with desired superhydrophobicity that can also be applied to various substrate materials. PMID:29308265

Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

NASA Astrophysics Data System (ADS)

Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

2015-08-01

Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm-2 or 1734 F g-1 at 5 mA cm-2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application.

Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

PubMed Central

Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

2015-01-01

Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm−2 or 1734 F g−1 at 5 mA cm−2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application. PMID:26278334

Hierarchical structure and dynamics of oligocarbonate-functionalized PEG block copolymer gels

NASA Astrophysics Data System (ADS)

Prabhu, Vivek; Wei, Guangmin; Ali, Samim; Venkataraman, Shrinivas; Yang, Yi Yan; Hedrick, James

Hierarchical, self-assembled block copolymers in aqueous solutions provide advanced materials for biomaterial applications. Recent advancements in the synthesis of aliphatic polycarbonates have shown nontraditional micellar and hierarchical structures driven by the supramolecular assembly of the carbonate block functionality that includes cholesterol, vitamin D, and fluorene. This presentation shall describe the supramolecular assembly structure and dynamics observed by static and dynamic light scattering, small-angle neutron scattering and transmission electron microscopy in a model pi-pi stacking driven fluorene system. The combination of real-space and reciprocal space methods to develop appropriate models that quantify the structure from the micelle to transient gel network will be discussed. 1) Biomedical Research Council, Agency for Science, Technology and Research, Singapore, 2) NIST Materials Genome Initiative.

A novel method for a multi-level hierarchical composite with brick-and-mortar structure

PubMed Central

Brandt, Kristina; Wolff, Michael F. H.; Salikov, Vitalij; Heinrich, Stefan; Schneider, Gerold A.

2013-01-01

The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships. PMID:23900554

A novel method for a multi-level hierarchical composite with brick-and-mortar structure.

PubMed

Brandt, Kristina; Wolff, Michael F H; Salikov, Vitalij; Heinrich, Stefan; Schneider, Gerold A

2013-01-01

The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships.

A novel method for a multi-level hierarchical composite with brick-and-mortar structure

NASA Astrophysics Data System (ADS)

Brandt, Kristina; Wolff, Michael F. H.; Salikov, Vitalij; Heinrich, Stefan; Schneider, Gerold A.

2013-07-01

The fascination for hierarchically structured hard tissues such as enamel or nacre arises from their unique structure-properties-relationship. During the last decades this numerously motivated the synthesis of composites, mimicking the brick-and-mortar structure of nacre. However, there is still a lack in synthetic engineering materials displaying a true hierarchical structure. Here, we present a novel multi-step processing route for anisotropic 2-level hierarchical composites by combining different coating techniques on different length scales. It comprises polymer-encapsulated ceramic particles as building blocks for the first level, followed by spouted bed spray granulation for a second level, and finally directional hot pressing to anisotropically consolidate the composite. The microstructure achieved reveals a brick-and-mortar hierarchical structure with distinct, however not yet optimized mechanical properties on each level. It opens up a completely new processing route for the synthesis of multi-level hierarchically structured composites, giving prospects to multi-functional structure-properties relationships.

Bio-inspired fabrication of stimuli-responsive photonic crystals with hierarchical structures and their applications

NASA Astrophysics Data System (ADS)

Lu, Tao; Peng, Wenhong; Zhu, Shenmin; Zhang, Di

2016-03-01

When the constitutive materials of photonic crystals (PCs) are stimuli-responsive, the resultant PCs exhibit optical properties that can be tuned by the stimuli. This can be exploited for promising applications in colour displays, biological and chemical sensors, inks and paints, and many optically active components. However, the preparation of the required photonic structures is the first issue to be solved. In the past two decades, approaches such as microfabrication and self-assembly have been developed to incorporate stimuli-responsive materials into existing periodic structures for the fabrication of PCs, either as the initial building blocks or as the surrounding matrix. Generally, the materials that respond to thermal, pH, chemical, optical, electrical, or magnetic stimuli are either soft or aggregate, which is why the manufacture of three-dimensional hierarchical photonic structures with responsive properties is a great challenge. Recently, inspired by biological PCs in nature which exhibit both flexible and responsive properties, researchers have developed various methods to synthesize metals and metal oxides with hierarchical structures by using a biological PC as the template. This review will focus on the recent developments in this field. In particular, PCs with biological hierarchical structures that can be tuned by external stimuli have recently been successfully fabricated. These findings offer innovative insights into the design of responsive PCs and should be of great importance for future applications of these materials.

Development of ultralight, super-elastic, hierarchical metallic meta-structures with i3DP technology

NASA Astrophysics Data System (ADS)

Zhang, Dongxing; Xiao, Junfeng; Moorlag, Carolyn; Guo, Qiuquan; Yang, Jun

2017-11-01

Lightweight and mechanically robust materials show promising applications in thermal insulation, energy absorption, and battery catalyst supports. This study demonstrates an effective method for creation of ultralight metallic structures based on initiator-integrated 3D printing technology (i3DP), which provides a possible platform to design the materials with the best geometric parameters and desired mechanical performance. In this study, ultralight Ni foams with 3D interconnected hollow tubes were fabricated, consisting of hierarchical features spanning three scale orders ranging from submicron to centimeter. The resultant materials can achieve an ultralight density of as low as 5.1 mg cm-3 and nearly recover after significant compression up to 50%. Due to a high compression ratio, the hierarchical structure exhibits superior properties in terms of energy absorption and mechanical efficiency. The relationship of structural parameters and mechanical response was established. The ability of achieving ultralight density <10 mg cm-3 and the stable \\bar{E}˜ {\\bar{ρ }}2 scaling through all range of relative density, indicates an advantage over the previous stochastic metal foams. Overall, this initiator-integrated 3D printing approach provides metallic structures with substantial benefits from the hierarchical design and fabrication flexibility to ultralight applications.

Hierarchical flexural strength of enamel: transition from brittle to damage-tolerant behaviour

PubMed Central

Bechtle, Sabine; Özcoban, Hüseyin; Lilleodden, Erica T.; Huber, Norbert; Schreyer, Andreas; Swain, Michael V.; Schneider, Gerold A.

2012-01-01

Hard, biological materials are generally hierarchically structured from the nano- to the macro-scale in a somewhat self-similar manner consisting of mineral units surrounded by a soft protein shell. Considerable efforts are underway to mimic such materials because of their structurally optimized mechanical functionality of being hard and stiff as well as damage-tolerant. However, it is unclear how different hierarchical levels interact to achieve this performance. In this study, we consider dental enamel as a representative, biological hierarchical structure and determine its flexural strength and elastic modulus at three levels of hierarchy using focused ion beam (FIB) prepared cantilevers of micrometre size. The results are compared and analysed using a theoretical model proposed by Jäger and Fratzl and developed by Gao and co-workers. Both properties decrease with increasing hierarchical dimension along with a switch in mechanical behaviour from linear-elastic to elastic-inelastic. We found Gao's model matched the results very well. PMID:22031729

Carbon with hierarchical pores from carbonized metal-organic frameworks for lithium sulphur batteries.

PubMed

Xi, Kai; Cao, Shuai; Peng, Xiaoyu; Ducati, Caterina; Kumar, R Vasant; Cheetham, Anthony K

2013-03-18

This paper presents a novel method and rationale for utilizing carbonized MOFs for sulphur loading to fabricate cathode structures for lithium-sulphur batteries. Unique carbon materials with differing hierarchical pore structures were synthesized from four types of zinc-containing metal-organic frameworks (MOFs). It is found that cathode materials made from MOFs-derived carbons with higher mesopore (2-50 nm) volumes exhibit increased initial discharge capacities, whereas carbons with higher micropore (<2 nm) volumes lead to cathode materials with better cycle stability.

Evading the strength–ductility trade-off dilemma in steel through gradient hierarchical nanotwins

PubMed Central

Wei, Yujie; Li, Yongqiang; Zhu, Lianchun; Liu, Yao; Lei, Xianqi; Wang, Gang; Wu, Yanxin; Mi, Zhenli; Liu, Jiabin; Wang, Hongtao; Gao, Huajian

2014-01-01

The strength–ductility trade-off has been a long-standing dilemma in materials science. This has limited the potential of many structural materials, steels in particular. Here we report a way of enhancing the strength of twinning-induced plasticity steel at no ductility trade-off. After applying torsion to cylindrical twinning-induced plasticity steel samples to generate a gradient nanotwinned structure along the radial direction, we find that the yielding strength of the material can be doubled at no reduction in ductility. It is shown that this evasion of strength–ductility trade-off is due to the formation of a gradient hierarchical nanotwinned structure during pre-torsion and subsequent tensile deformation. A series of finite element simulations based on crystal plasticity are performed to understand why the gradient twin structure can cause strengthening and ductility retention, and how sequential torsion and tension lead to the observed hierarchical nanotwinned structure through activation of different twinning systems. PMID:24686581

Hierarchical Porous Carbon Materials Derived from Sheep Manure for High-Capacity Supercapacitors.

PubMed

Zhang, Caiyun; Zhu, Xiaohong; Cao, Min; Li, Menglin; Li, Na; Lai, Liuqin; Zhu, Jiliang; Wei, Dacheng

2016-05-10

3 D capacitance: Hierarchical porous carbon-based electrode materials with a composite structure are prepared from a biomass waste by a facile carbonization and activation process without using any additional templates. Benefiting from the composite structure, the ions experience a variety of environments, which contribute significantly to the excellent electrochemical properties of supercapacitors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical LiFePO4 with a controllable growth of the (010) facet for lithium-ion batteries.

PubMed

Guo, Binbin; Ruan, Hongcheng; Zheng, Cheng; Fei, Hailong; Wei, Mingdeng

2013-09-27

Hierarchically structured LiFePO4 was successfully synthesized by ionic liquid solvothermal method. These hierarchically structured LiFePO4 samples were constructed from nanostructured platelets with their (010) facets mainly exposed. To the best of our knowledge, facet control of a hierarchical LiFePO4 crystal has not been reported yet. Based on a series of experimental results, a tentative mechanism for the formation of these hierarchical structures was proposed. After these hierarchically structured LiFePO4 samples were coated with a thin carbon layer and used as cathode materials for lithium-ion batteries, they exhibited excellent high-rate discharge capability and cycling stability. For instance, a capacity of 95% can be maintained for the LiFePO4 sample at a rate as high as 20 C, even after 1000 cycles.

Bioinspired Thermoresponsive Photonic Polymers with Hierarchical Structures and Their Unique Properties.

PubMed

Lu, Tao; Zhu, Shenmin; Ma, Jun; Lin, Jinyou; Wang, Wanlin; Pan, Hui; Tian, Feng; Zhang, Wang; Zhang, Di

2015-10-01

Thermoresponsive photonic materials having hierarchical structures are created by combining a template of Morpho butterfly wings with poly(N-isopropylacrylamide) (PNIPAM) through a chemical bonding and polymerization route. These materials show temperature-induced color tunability. Through reacting with both NIPAM monomers and the amino groups of chitosan in wing scales, glutaraldehyde workes as a bridge by creating chemical bonding between the biotemplate and the PNIPAM. The corresponding reflection peaks red-shift with increase in temperature-an opposite phenomenon to previous studies, demonstrating a thermoresponsive photonic property. This unique phenomenon is caused by the refractive index change due to the volume change of PNIPAM during the temperature rising. This work sets up an efficient strategy for the fabrication of stimuli-responsive photonic materials with hierarchical structures toward extensive applications in science and technology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical Model for the Analysis of Scattering Data of Complex Materials

DOE PAGES

Oyedele, Akinola; Mcnutt, Nicholas W.; Rios, Orlando; ...

2016-05-16

Interpreting the results of scattering data for complex materials with a hierarchical structure in which at least one phase is amorphous presents a significant challenge. Often the interpretation relies on the use of large-scale molecular dynamics (MD) simulations, in which a structure is hypothesized and from which a radial distribution function (RDF) can be extracted and directly compared against an experimental RDF. This computationally intensive approach presents a bottleneck in the efficient characterization of the atomic structure of new materials. Here, we propose and demonstrate an approach for a hierarchical decomposition of the RDF in which MD simulations are replacedmore » by a combination of tractable models and theory at the atomic scale and the mesoscale, which when combined yield the RDF. We apply the procedure to a carbon composite, in which graphitic nanocrystallites are distributed in an amorphous domain. We compare the model with the RDF from both MD simulation and neutron scattering data. Ultimately, this procedure is applicable for understanding the fundamental processing-structure-property relationships in complex magnetic materials.« less

A Facile Method to Fabricate Anisotropic Hydrogels with Perfectly Aligned Hierarchical Fibrous Structures.

PubMed

Mredha, Md Tariful Islam; Guo, Yun Zhou; Nonoyama, Takayuki; Nakajima, Tasuku; Kurokawa, Takayuki; Gong, Jian Ping

2018-03-01

Natural structural materials (such as tendons and ligaments) are comprised of multiscale hierarchical architectures, with dimensions ranging from nano- to macroscale, which are difficult to mimic synthetically. Here a bioinspired, facile method to fabricate anisotropic hydrogels with perfectly aligned multiscale hierarchical fibrous structures similar to those of tendons and ligaments is reported. The method includes drying a diluted physical hydrogel in air by confining its length direction. During this process, sufficiently high tensile stress is built along the length direction to align the polymer chains and multiscale fibrous structures (from nano- to submicro- to microscale) are spontaneously formed in the bulk material, which are well-retained in the reswollen gel. The method is useful for relatively rigid polymers (such as alginate and cellulose), which are susceptible to mechanical signal. By controlling the drying with or without prestretching, the degree of alignment, size of superstructures, and the strength of supramolecular interactions can be tuned, which sensitively influence the strength and toughness of the hydrogels. The mechanical properties are comparable with those of natural ligaments. This study provides a general strategy for designing hydrogels with highly ordered hierarchical structures, which opens routes for the development of many functional biomimetic materials for biomedical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchically structured lithium titanate for ultrafast charging in long-life high capacity batteries

NASA Astrophysics Data System (ADS)

Odziomek, Mateusz; Chaput, Frédéric; Rutkowska, Anna; Świerczek, Konrad; Olszewska, Danuta; Sitarz, Maciej; Lerouge, Frédéric; Parola, Stephane

2017-05-01

High-performance Li-ion batteries require materials with well-designed and controlled structures on nanometre and micrometre scales. Electrochemical properties can be enhanced by reducing crystallite size and by manipulating structure and morphology. Here we show a method for preparing hierarchically structured Li4Ti5O12 yielding nano- and microstructure well-suited for use in lithium-ion batteries. Scalable glycothermal synthesis yields well-crystallized primary 4-8 nm nanoparticles, assembled into porous secondary particles. X-ray photoelectron spectroscopy reveals presence of Ti+4 only; combined with chemical analysis showing lithium deficiency, this suggests oxygen non-stoichiometry. Electron microscopy confirms hierarchical morphology of the obtained material. Extended cycling tests in half cells demonstrates capacity of 170 mAh g-1 and no sign of capacity fading after 1,000 cycles at 50C rate (charging completed in 72 s). The particular combination of nanostructure, microstructure and non-stoichiometry for the prepared lithium titanate is believed to underlie the observed electrochemical performance of material.

Bioinspired Single-Walled Carbon Nanotubes as a Spider Silk Structure for Ultrahigh Mechanical Property.

PubMed

Luo, Chengzhi; Li, Fangying; Li, Delong; Fu, Qiang; Pan, Chunxu

2016-11-16

Due to its unique hierarchical structure, natural spider silk features exceptional mechanical properties such as high tensile strength and great extensibility, making it one of the toughest materials. Herein, we design bioinspired spider silk single-walled carbon nanotubes (BISS-SWCNTs) that combine the hierarchical structure of spider silk and the high strength and conductivity of SWCNTs. To imitate the hierarchical structure, Fe nanoparticles are embedded on the surface of directly synthesized SWCNTs skeleton followed by coating an amorphous carbon layer. The carbon layer forms the spider silk-featured skin-core structure with SWCNTs, thus making the tube junction tougher. The embedded Fe nanoparticles act as glue spots for preventing interfacial slippages between the BISS-SWCNTs and the reinforced matrix. With only 2.1 wt % BISS-SWCNTs added, the tensile strength and Young's modulus of the BISS-SWCNTs/PMMA composites can be improved by 300%. More importantly, the BISS-SWCNTs also retain the high conductivity and transmittance of the pristine SWCNTs film. This unique bioinspired material will be of great importance in applications of multifunctional composite materials and has important implications for the future of biomimetic materials.

Efficient Flame Detection and Early Warning Sensors on Combustible Materials Using Hierarchical Graphene Oxide/Silicone Coatings.

PubMed

Wu, Qian; Gong, Li-Xiu; Li, Yang; Cao, Cheng-Fei; Tang, Long-Cheng; Wu, Lianbin; Zhao, Li; Zhang, Guo-Dong; Li, Shi-Neng; Gao, Jiefeng; Li, Yongjin; Mai, Yiu-Wing

2018-01-23

Design and development of smart sensors for rapid flame detection in postcombustion and early fire warning in precombustion situations are critically needed to improve the fire safety of combustible materials in many applications. Herein, we describe the fabrication of hierarchical coatings created by assembling a multilayered graphene oxide (GO)/silicone structure onto different combustible substrate materials. The resulting coatings exhibit distinct temperature-responsive electrical resistance change as efficient early warning sensors for detecting abnormal high environmental temperature, thus enabling fire prevention below the ignition temperature of combustible materials. After encountering a flame attack, we demonstrate extremely rapid flame detection response in 2-3 s and excellent flame self-extinguishing retardancy for the multilayered GO/silicone structure that can be synergistically transformed to a multiscale graphene/nanosilica protection layer. The hierarchical coatings developed are promising for fire prevention and protection applications in various critical fire risk and related perilous circumstances.

Hierarchically structured transparent hybrid membranes by in situ growth of mesostructured organosilica in host polymer

NASA Astrophysics Data System (ADS)

Vallé, Karine; Belleville, Philippe; Pereira, Franck; Sanchez, Clément

2006-02-01

The elaborate performances characterizing natural materials result from functional hierarchical constructions at scales ranging from nanometres to millimetres, each construction allowing the material to fit the physical or chemical demands occurring at these different levels. Hierarchically structured materials start to demonstrate a high input in numerous promising applied domains such as sensors, catalysis, optics, fuel cells, smart biologic and cosmetic vectors. In particular, hierarchical hybrid materials permit the accommodation of a maximum of elementary functions in a small volume, thereby optimizing complementary possibilities and properties between inorganic and organic components. The reported strategies combine sol-gel chemistry, self-assembly routes using templates that tune the material's architecture and texture with the use of larger inorganic, organic or biological templates such as latex, organogelator-derived fibres, nanolithographic techniques or controlled phase separation. We propose an approach to forming transparent hierarchical hybrid functionalized membranes using in situ generation of mesostructured hybrid phases inside a non-porogenic hydrophobic polymeric host matrix. We demonstrate that the control of the multiple affinities existing between organic and inorganic components allows us to design the length-scale partitioning of hybrid nanomaterials with tuned functionalities and desirable size organization from ångström to centimetre. After functionalization of the mesoporous hybrid silica component, the resulting membranes have good ionic conductivity offering interesting perspectives for the design of solid electrolytes, fuel cells and other ion-transport microdevices.

Silica biomineralization via the self-assembly of helical biomolecules.

PubMed

Liu, Ben; Cao, Yuanyuan; Huang, Zhehao; Duan, Yingying; Che, Shunai

2015-01-21

The biomimetic synthesis of relevant silica materials using biological macromolecules as templates via silica biomineralization processes attract rapidly rising attention toward natural and artificial materials. Biomimetic synthesis studies are useful for improving the understanding of the formation mechanism of the hierarchical structures found in living organisms (such as diatoms and sponges) and for promoting significant developments in the biotechnology, nanotechnology and materials chemistry fields. Chirality is a ubiquitous phenomenon in nature and is an inherent feature of biomolecular components in organisms. Helical biomolecules, one of the most important types of chiral macromolecules, can self-assemble into multiple liquid-crystal structures and be used as biotemplates for silica biomineralization, which renders them particularly useful for fabricating complex silica materials under ambient conditions. Over the past two decades, many new silica materials with hierarchical structures and complex morphologies have been created using helical biomolecules. In this review, the developments in this field are described and the recent progress in silica biomineralization templating using several classes of helical biomolecules, including DNA, polypeptides, cellulose and rod-like viruses is summarized. Particular focus is placed on the formation mechanism of biomolecule-silica materials (BSMs) with hierarchical structures. Finally, current research challenges and future developments are discussed in the conclusion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical photonic structured stimuli-responsive materials as high-performance colorimetric sensors

NASA Astrophysics Data System (ADS)

Lu, Tao; Zhu, Shenmin; Chen, Zhixin; Wang, Wanlin; Zhang, Wang; Zhang, Di

2016-05-01

Hierarchical photonic structures in nature are of special interest because they can be used as templates for fabrication of stimuli-responsive photonic crystals (PCs) with unique structures beyond man-made synthesis. The current stimuli-responsive PCs templated directly from natural PCs showed a very weak external stimuli response and poor durability due to the limitations of natural templates. Herein, we tackle this problem by chemically coating functional polymers, polyacrylamide, on butterfly wing scales which have hierarchical photonic structures. As a result of the combination of the strong water absorption properties of the polyacrylamide and the PC structures of the butterfly wing scales, the designed materials demonstrated excellent humidity responsive properties and a tremendous colour change. The colour change is induced by the refractive index change which is in turn due to the swollen nature of the polymer when the relative humidity changes. The butterfly wing scales also showed an excellent durability which is due to the chemical bonds formed between the polymer and wing scales. The synthesis strategy provides an avenue for the promising applications of stimuli-responsive PCs with hierarchical structures.Hierarchical photonic structures in nature are of special interest because they can be used as templates for fabrication of stimuli-responsive photonic crystals (PCs) with unique structures beyond man-made synthesis. The current stimuli-responsive PCs templated directly from natural PCs showed a very weak external stimuli response and poor durability due to the limitations of natural templates. Herein, we tackle this problem by chemically coating functional polymers, polyacrylamide, on butterfly wing scales which have hierarchical photonic structures. As a result of the combination of the strong water absorption properties of the polyacrylamide and the PC structures of the butterfly wing scales, the designed materials demonstrated excellent humidity responsive properties and a tremendous colour change. The colour change is induced by the refractive index change which is in turn due to the swollen nature of the polymer when the relative humidity changes. The butterfly wing scales also showed an excellent durability which is due to the chemical bonds formed between the polymer and wing scales. The synthesis strategy provides an avenue for the promising applications of stimuli-responsive PCs with hierarchical structures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01875k

Intrinsic hierarchical structural imperfections in a natural ceramic of bivalve shell with distinctly graded properties

PubMed Central

Jiao, Da; Liu, Zengqian; Zhang, Zhenjun; Zhang, Zhefeng

2015-01-01

Despite the extensive investigation on the structure of natural biological materials, insufficient attention has been paid to the structural imperfections by which the mechanical properties of synthetic materials are dominated. In this study, the structure of bivalve Saxidomus purpuratus shell has been systematically characterized quantitatively on multiple length scales from millimeter to sub-nanometer. It is revealed that hierarchical imperfections are intrinsically involved in the crossed-lamellar structure of the shell despite its periodically packed platelets. In particular, various favorable characters which are always pursued in synthetic materials, e.g. nanotwins and low-angle misorientations, have been incorporated herein. The possible contributions of these imperfections to mechanical properties are further discussed. It is suggested that the imperfections may serve as structural adaptations, rather than detrimental defects in the real sense, to help improve the mechanical properties of natural biological materials. This study may aid in understanding the optimizing strategies of structure and properties designed by nature, and accordingly, provide inspiration for the design of synthetic materials. PMID:26198844

Intrinsic hierarchical structural imperfections in a natural ceramic of bivalve shell with distinctly graded properties.

PubMed

Jiao, Da; Liu, Zengqian; Zhang, Zhenjun; Zhang, Zhefeng

2015-07-22

Despite the extensive investigation on the structure of natural biological materials, insufficient attention has been paid to the structural imperfections by which the mechanical properties of synthetic materials are dominated. In this study, the structure of bivalve Saxidomus purpuratus shell has been systematically characterized quantitatively on multiple length scales from millimeter to sub-nanometer. It is revealed that hierarchical imperfections are intrinsically involved in the crossed-lamellar structure of the shell despite its periodically packed platelets. In particular, various favorable characters which are always pursued in synthetic materials, e.g. nanotwins and low-angle misorientations, have been incorporated herein. The possible contributions of these imperfections to mechanical properties are further discussed. It is suggested that the imperfections may serve as structural adaptations, rather than detrimental defects in the real sense, to help improve the mechanical properties of natural biological materials. This study may aid in understanding the optimizing strategies of structure and properties designed by nature, and accordingly, provide inspiration for the design of synthetic materials.

Functional adaptation of crustacean exoskeletal elements through structural and compositional diversity: a combined experimental and theoretical study.

PubMed

Fabritius, Helge-Otto; Ziegler, Andreas; Friák, Martin; Nikolov, Svetoslav; Huber, Julia; Seidl, Bastian H M; Ruangchai, Sukhum; Alagboso, Francisca I; Karsten, Simone; Lu, Jin; Janus, Anna M; Petrov, Michal; Zhu, Li-Fang; Hemzalová, Pavlína; Hild, Sabine; Raabe, Dierk; Neugebauer, Jörg

2016-09-09

The crustacean cuticle is a composite material that covers the whole animal and forms the continuous exoskeleton. Nano-fibers composed of chitin and protein molecules form most of the organic matrix of the cuticle that, at the macroscale, is organized in up to eight hierarchical levels. At least two of them, the exo- and endocuticle, contain a mineral phase of mainly Mg-calcite, amorphous calcium carbonate and phosphate. The high number of hierarchical levels and the compositional diversity provide a high degree of freedom for varying the physical, in particular mechanical, properties of the material. This makes the cuticle a versatile material ideally suited to form a variety of skeletal elements that are adapted to different functions and the eco-physiological strains of individual species. This review presents our recent analytical, experimental and theoretical studies on the cuticle, summarising at which hierarchical levels structure and composition are modified to achieve the required physical properties. We describe our multi-scale hierarchical modeling approach based on the results from these studies, aiming at systematically predicting the structure-composition-property relations of cuticle composites from the molecular level to the macro-scale. This modeling approach provides a tool to facilitate the development of optimized biomimetic materials within a knowledge-based design approach.

Microfabrication of hierarchical structures for engineered mechanical materials

NASA Astrophysics Data System (ADS)

Vera Canudas, Marc

Materials found in nature present, in some cases, unique properties from their constituents that are of great interest in engineered materials for applications ranging from structural materials for the construction of bridges, canals and buildings to the fabrication of new lightweight composites for airplane and automotive bodies, to protective thin film coatings, amongst other fields. Research in the growing field of biomimetic materials indicates that the micro-architectures present in natural materials are critical to their macroscopic mechanical properties. A better understanding of the effect that structure and hierarchy across scales have on the material properties will enable engineered materials with enhanced properties. At the moment, very few theoretical models predict mechanical properties of simple materials based on their microstructures. Moreover these models are based on observations from complex biological systems. One way to overcome this challenge is through the use of microfabrication techniques to design and fabricate simple materials, more appropriate for the study of hierarchical organizations and microstructured materials. Arrays of structures with controlled geometry and dimension can be designed and fabricated at different length scales, ranging from a few hundred nanometers to centimeters, in order to mimic similar systems found in nature. In this thesis, materials have been fabricated in order to gain fundamental insight into the complex hierarchical materials found in nature and to engineer novel materials with enhanced mechanical properties. The materials fabricated here were mechanically characterized and compared to simple mechanics models to describe their behavior with the goal of applying the knowledge acquired to the design and synthesis of future engineered materials with novel properties.

Self Assembled Structures by Directional Solidification of Eutectics

NASA Technical Reports Server (NTRS)

Dynys, Frederick W.; Sayir, Ali

2004-01-01

Interest in ordered porous structures has grown because of there unique properties such as photonic bandgaps, high backing packing density and high surface to volume ratio. Inspired by nature, biometric strategies using self assembled organic molecules dominate the development of hierarchical inorganic structures. Directional solidification of eutectics (DSE) also exhibit self assembly characteristics to form hierarchical metallic and inorganic structures. Crystallization of diphasic materials by DSE can produce two dimensional ordered structures consisting of rods or lamella. By selective removal of phases, DSE is capable to fabricate ordered pore arrays or ordered pin arrays. Criteria and limitations to fabricate hierarchical structures will be presented. Porous structures in silicon base alloys and ceramic systems will be reported.

Enhanced lithium storage performances of hierarchical hollow MoS₂ nanoparticles assembled from nanosheets.

PubMed

Wang, Meng; Li, Guangda; Xu, Huayun; Qian, Yitai; Yang, Jian

2013-02-01

MoS(2), because of its layered structure and high theoretical capacity, has been regarded as a potential candidate for electrode materials in lithium secondary batteries. But it suffers from the poor cycling stability and low rate capability. Here, hierarchical hollow nanoparticles of MoS(2) nanosheets with an increased interlayer distance are synthesized by a simple solvothermal reaction at a low temperature. The formation of hierarchical hollow nanoparticles is based on the intermediate, K(2)NaMoO(3)F(3), as a self-sacrificed template. These hollow nanoparticles exhibit a reversible capacity of 902 mA h g(-1) at 100 mA g(-1) after 80 cycles, much higher than the solid counterpart. At a current density of 1000 mA g(-1), the reversible capacity of the hierarchical hollow nanoparticles could be still maintained at 780 mAh g(-1). The enhanced lithium storage performances of the hierarchical hollow nanoparticles in reversible capacities, cycling stability and rate performances can be attributed to their hierarchical surface, hollow structure feature and increased layer distance of S-Mo-S. Hierarchical hollow nanoparticles as an ensemble of these features, could be applied to other electrode materials for the superior electrochemical performance.

A novel snowflake-like SnO2 hierarchical architecture with superior gas sensing properties

NASA Astrophysics Data System (ADS)

Li, Yanqiong

2018-02-01

Snowflake-like SnO2 hierarchical architecture has been synthesized via a facile hydrothermal method and followed by calcination. The SnO2 hierarchical structures are assembled with thin nanoflakes blocks, which look like snowflake shape. A possible mechanism for the formation of the SnO2 hierarchical structures is speculated. Moreover, gas sensing tests show that the sensor based on snowflake-like SnO2 architectures exhibited excellent gas sensing properties. The enhancement may be attributed to its unique structures, in which the porous feature on the snowflake surface could further increase the active surface area of the materials and provide facile pathways for the target gas.

CuO-Decorated ZnO Hierarchical Nanostructures as Efficient and Established Sensing Materials for H2S Gas Sensors

PubMed Central

Vuong, Nguyen Minh; Chinh, Nguyen Duc; Huy, Bui The; Lee, Yong-Ill

2016-01-01

Highly sensitive hydrogen sulfide (H2S) gas sensors were developed from CuO-decorated ZnO semiconducting hierarchical nanostructures. The ZnO hierarchical nanostructure was fabricated by an electrospinning method following hydrothermal and heat treatment. CuO decoration of ZnO hierarchical structures was carried out by a wet method. The H2S gas-sensing properties were examined at different working temperatures using various quantities of CuO as the variable. CuO decoration of the ZnO hierarchical structure was observed to promote sensitivity for H2S gas higher than 30 times at low working temperature (200 °C) compared with that in the nondecorated hierarchical structure. The sensing mechanism of the hybrid sensor structure is also discussed. The morphology and characteristics of the samples were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis absorption, photoluminescence (PL), and electrical measurements. PMID:27231026

Monodisperse Carbon Nanospheres with Hierarchical Porous Structure as Electrode Material for Supercapacitor

NASA Astrophysics Data System (ADS)

Yang, Xiutao; Xia, Hui; Liang, Zhongguan; Li, Haiyan; Yu, Hongwen

2017-09-01

Carbon nanospheres with distinguishable microstructure were prepared by carbonization and subsequent KOH activation of F108/resorcinol-formaldehyde composites. The dosage of triblock copolymer Pluronic F108 is crucial to the microstructure differences. With the adding of F108, the polydisperse carbon nanospheres (PCNS) with microporous structure, monodisperse carbon nanospheres (MCNS) with hierarchical porous structure, and agglomerated carbon nanospheres (ACNS) were obtained. Their microstructure and capacitance properties were carefully compared. As a result of the synergetic effect of mono-dispersion spheres and hierarchical porous structures, the MCNS sample shows improved electrochemical performance, i.e., the highest specific capacitance of 224 F g-1 (0.2 A g-1), the best rate capability (73% retention at 20 A g-1), and the most excellent capacitance retention of 93% over 10,000 cycles, making it to be the promising electrode material for high-performance supercapacitors.

One-Pot Synthesis of Lithium-Rich Cathode Material with Hierarchical Morphology.

PubMed

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Liberti, Emanuela; Allen, Christopher S; Kirkland, Angus I; Bruce, Peter G

2016-12-14

Lithium-rich transition metal oxides, Li 1+x TM 1-x O 2 (TM, transition metal), have attracted much attention as potential candidate cathode materials for next generation lithium ion batteries because their high theoretical capacity. Here we present the synthesis of Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 using a facile one-pot resorcinol-formaldehyde method. Structural characterization indicates that the material adopts a hierarchical porous morphology consisting of uniformly distributed small pores and disordered large pore structures. The material exhibits excellent electrochemical cycling stability and a good retention of capacity at high rates. The material has been shown to be both advantageous in terms of gravimetric and volumetric capacities over state of the art commercial cathode materials.

Biological materials by design.

PubMed

Qin, Zhao; Dimas, Leon; Adler, David; Bratzel, Graham; Buehler, Markus J

2014-02-19

In this topical review we discuss recent advances in the use of physical insight into the way biological materials function, to design novel engineered materials 'from scratch', or from the level of fundamental building blocks upwards and by using computational multiscale methods that link chemistry to material function. We present studies that connect advances in multiscale hierarchical material structuring with material synthesis and testing, review case studies of wood and other biological materials, and illustrate how engineered fiber composites and bulk materials are designed, modeled, and then synthesized and tested experimentally. The integration of experiment and simulation in multiscale design opens new avenues to explore the physics of materials from a fundamental perspective, and using complementary strengths from models and empirical techniques. Recent developments in this field illustrate a new paradigm by which complex material functionality is achieved through hierarchical structuring in spite of simple material constituents.

Development of new smart materials and spinning systems inspired by natural silks and their applications

NASA Astrophysics Data System (ADS)

Cheng, Jie; Lee, Sang-Hoon

2015-12-01

Silks produced by spiders and silkworms are charming natural biological materials with highly optimized hierarchical structures and outstanding physicomechanical properties. The superior performance of silks relies on the integration of a unique protein sequence, a distinctive spinning process, and complex hierarchical structures. Silks have been prepared to form a variety of morphologies and are widely used in diverse applications, for example, in the textile industry, as drug delivery vehicles, and as tissue engineering scaffolds. This review presents an overview of the organization of natural silks, in which chemical and physical functions are optimized, as well as a range of new materials inspired by the desire to mimic natural silk structure and synthesis.

The Origin of Hierarchical Structure in Self-Assembled Graphene Oxide Papers and the Effect on Mechanical Properties

NASA Astrophysics Data System (ADS)

Nandy, Krishanu

The quest for new materials with ever improving properties has motivated interest in bulk nanostructured materials. Graphene, a two-dimensional sheet of hexagonally arranged carbon atoms, has been of particular interest given its exceptional mechanical, thermal, optical and electrical properties. Graphene oxide is a chemically modified form of graphene in which the honeycomb lattice of carbon atoms is decorated with oxygen bearing functional groups. Graphene oxide represents a facile route for the production of large quantities of graphene based materials, is stable in aqueous and polar organic solvents and has the potential for further chemical modification. In this dissertation, the origin and influence of hierarchical structure on the mechanical properties of graphene oxide paper and graphene oxide paper based materials has been investigated. Free-standing papers derived from graphene oxide are of interest as structural materials due to their impressive mechanical properties. While studies have investigated the mechanical properties of graphene oxide papers, little is known about the formation mechanism. Using a series of flash-freezing experiments on graphene oxide papers undergoing formation, a stop-motion animation of the fabrication process was obtained. The results explain the origin of the hierarchical nature of graphene oxide papers and provide a method for the tailoring of graphene oxide based materials. An in depth study of fusion of graphene oxide papers demonstrates a simple single-step route for the fabrication of practical materials derived from graphene oxide papers. Fused papers retain the properties of constituent papers allowing for the fabrication of mechanical heterostructures that replicate the hierarchical nature of natural materials. The contribution of the hierarchical nature of graphene oxide papers to the mechanical properties was examined by comparing papers formed by two different mechanisms. The intermediate length scale structures were found to play a key role in yielding tough papers with high failure stress. Finally, efforts to investigate the microstructural mechanisms that govern the mechanical properties of graphene oxide papers by 3D printing of a tensile tester are detailed. It is intended to release the design of the tensile tester to the community in an effort to reduce cost and improve availability of lab equipment.

Biominerals- hierarchical nanocomposites: the example of bone

PubMed Central

Beniash, Elia

2010-01-01

Many organisms incorporate inorganic solids in their tissues to enhance their functional, primarily mechanical, properties. These mineralized tissues, also called biominerals, are unique organo-mineral nanocomposites, organized at several hierarchical levels, from nano- to macroscale. Unlike man made composite materials, which often are simple physical blends of their components, the organic and inorganic phases in biominerals interface at the molecular level. Although these tissues are made of relatively weak components at ambient conditions, their hierarchical structural organization and intimate interactions between different elements lead to superior mechanical properties. Understanding basic principles of formation, structure and functional properties of these tissues might lead to novel bioinspired strategies for material design and better treatments for diseases of the mineralized tissues. This review focuses on general principles of structural organization, formation and functional properties of biominerals on the example the bone tissues. PMID:20827739

Flexible supercapacitors with high areal capacitance based on hierarchical carbon tubular nanostructures

NASA Astrophysics Data System (ADS)

Zhang, Haitao; Su, Hai; Zhang, Lei; Zhang, Binbin; Chun, Fengjun; Chu, Xiang; He, Weidong; Yang, Weiqing

2016-11-01

Hierarchical structure design can greatly enhance the unique properties of primary material(s) but suffers from complicated preparation process and difficult self-assembly of materials with different dimensionalities. Here we report on the growth of single carbon tubular nanostructures with hierarchical structure (hCTNs) through a simple method based on direct conversion of carbon dioxide. Resorting to in-situ transformation and self-assembly of carbon micro/nano-structures, the obtained hCTNs are blood-like multichannel hierarchy composed of one large channel across the hCTNs and plenty of small branches connected to each other. Due to the unique pore structure and high surface area, these hCTN-based flexible supercapacitors possess the highest areal capacitance of ∼320 mF cm-2, as well as good rate-capability and excellent cycling stability (95% retention after 2500 cycles). It was established that this method can control the morphology, size, and density of hCTNs and effectively construct hCTNs well anchored to the various substrates. Our work unambiguously demonstrated the potential of hCTNs for large flexible supercapacitors and integrated energy management electronics.

Hierarchical Materials Design by Pattern Transfer Printing of Self-Assembled Binary Nanocrystal Superlattices

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

Paik, Taejong; Yun, Hongseok; Fleury, Blaise

We demonstrate the fabrication of hierarchical materials by controlling the structure of highly ordered binary nanocrystal superlattices (BNSLs) on multiple length scales. Combinations of magnetic, plasmonic, semiconducting, and insulating colloidal nanocrystal (NC) building blocks are self-assembled into BNSL membranes via the liquid–interfacial assembly technique. Free-standing BNSL membranes are transferred onto topographically structured poly(dimethylsiloxane) molds via the Langmuir–Schaefer technique and then deposited in patterns onto substrates via transfer printing. BNSLs with different structural motifs are successfully patterned into various meso- and microstructures such as lines, circles, and even three-dimensional grids across large-area substrates. A combination of electron microscopy and grazing incidencemore » small-angle X-ray scattering (GISAXS) measurements confirm the ordering of NC building blocks in meso- and micropatterned BNSLs. This technique demonstrates structural diversity in the design of hierarchical materials by assembling BNSLs from NC building blocks of different composition and size by patterning BNSLs into various size and shape superstructures of interest for a broad range of applications.« less

Correlation between the hierarchical structures and nanomechanical properties of amyloid fibrils

NASA Astrophysics Data System (ADS)

Lee, Gyudo; Lee, Wonseok; Baik, Seunghyun; Kim, Yong Ho; Eom, Kilho; Kwon, Taeyun

2018-07-01

Amyloid fibrils have recently been highlighted due to their excellent mechanical properties, which not only play a role in their biological functions but also imply their applications in biomimetic material design. Despite recent efforts to unveil how the excellent mechanical properties of amyloid fibrils originate, it has remained elusive how the anisotropic nanomechanical properties of hierarchically structured amyloid fibrils are determined. Here, we characterize the anisotropic nanomechanical properties of hierarchically structured amyloid fibrils using atomic force microscopy experiments and atomistic simulations. It is shown that the hierarchical structure of amyloid fibrils plays a crucial role in determining their radial elastic property but does not make any effect on their bending elastic property. This is attributed to the role of intermolecular force acting between the filaments (constituting the fibril) on the radial elastic modulus of amyloid fibrils. Our finding illustrates how the hierarchical structure of amyloid fibrils encodes their anisotropic nanomechanical properties. Our study provides key design principles of amyloid fibrils, which endow valuable insight into the underlying mechanisms of amyloid mechanics.

A novel multifunctional NiTi/Ag hierarchical composite

PubMed Central

Hao, Shijie; Cui, Lishan; Jiang, Jiang; Guo, Fangmin; Xiao, Xianghui; Jiang, Daqiang; Yu, Cun; Chen, Zonghai; Zhou, Hua; Wang, Yandong; Liu, YuZi; Brown, Dennis E.; Ren, Yang

2014-01-01

Creating multifunctional materials is an eternal goal of mankind. As the properties of monolithic materials are necessary limited, one route to extending them is to create a composite by combining contrasting materials. The potential of this approach is neatly illustrated by the formation of nature materials where contrasting components are combined in sophisticated hierarchical designs. In this study, inspired by the hierarchical structure of the tendon, we fabricated a novel composite by subtly combining two contrasting components: NiTi shape-memory alloy and Ag. The composite exhibits simultaneously exceptional mechanical properties of high strength, good superelasticity and high mechanical damping, and remarkable functional properties of high electric conductivity, high visibility under fluoroscopy and excellent thermal-driven ability. All of these result from the effective-synergy between the NiTi and Ag components, and place the composite in a unique position in the properties chart of all known structural-functional materials providing new opportunities for innovative electrical, mechanical and biomedical applications. Furthermore, this work may open new avenues for designing and fabricating advanced multifunctional materials by subtly combining contrasting multi-components. PMID:24919945

Hierarchical Mesoporous Lithium-Rich Li[Li0.2Ni0.2Mn0.6]O2 Cathode Material Synthesized via Ice Templating for Lithium-Ion Battery.

PubMed

Li, Yu; Wu, Chuan; Bai, Ying; Liu, Lu; Wang, Hui; Wu, Feng; Zhang, Na; Zou, Yufeng

2016-07-27

Tuning hierarchical micro/nanostructure of electrode materials is a sought-after means to reinforce their electrochemical performance in the energy storage field. Herein, we introduce a type of hierarchical mesoporous Li[Li0.2Ni0.2Mn0.6]O2 microsphere composed of nanoparticles synthesized via an ice templating combined coprecipitation strategy. It is a low-cost, eco-friendly, and easily operated method using ice as a template to control material with homogeneous morphology and rich porous channels. The as-prepared material exhibits remarkably enhanced electrochemical performances with higher capacity, more excellent cycling stability and more superior rate property, compared with the sample prepared by conventional coprecipitation method. It has satisfactory initial discharge capacities of 280.1 mAh g(-1) at 0.1 C, 207.1 mAh g(-1) at 2 C, and 152.4 mAh g(-1) at 5 C, as well as good cycle performance. The enhanced electrochemical performance can be ascribed to the stable hierarchical microsized structure and the improved lithium-ion diffusion kinetics from the highly porous structure.

Integrated Design and Simulation of Tunable, Multi-State Structures Fabricated Monolithically with Multi-Material 3D Printing.

PubMed

Chen, Tian; Mueller, Jochen; Shea, Kristina

2017-03-31

Multi-material 3D printing has created new opportunities for fabricating deployable structures. We design reversible, deployable structures that are fabricated flat, have defined load bearing capacity, and multiple, predictable activated geometries. These structures are designed with a hierarchical framework where the proposed bistable actuator serves as the base building block. The actuator is designed to maximise its stroke length, with the expansion ratio approaching one when serially connected. The activation force of the actuator is parameterised through its joint material and joint length. Simulation and experimental results show that the bistability triggering force can be tuned between 0.5 and 5.0 N. Incorporating this bistable actuator, the first group of hierarchical designs demonstrate the deployment of space frame structures with a tetrahedron module consisting of three active edges, each containing four serially connected actuators. The second group shows the design of flat structures that assume either positive or negative Gaussian curvature once activated. By flipping the initial configuration of the unit actuators, structures such as a dome and an enclosure are demonstrated. A modified Dynamic Relaxation method is used to simulate all possible geometries of the hierarchical structures. Measured geometries differ by less than 5% compared to simulation results.

Integrated Design and Simulation of Tunable, Multi-State Structures Fabricated Monolithically with Multi-Material 3D Printing

PubMed Central

Chen, Tian; Mueller, Jochen; Shea, Kristina

2017-01-01

Multi-material 3D printing has created new opportunities for fabricating deployable structures. We design reversible, deployable structures that are fabricated flat, have defined load bearing capacity, and multiple, predictable activated geometries. These structures are designed with a hierarchical framework where the proposed bistable actuator serves as the base building block. The actuator is designed to maximise its stroke length, with the expansion ratio approaching one when serially connected. The activation force of the actuator is parameterised through its joint material and joint length. Simulation and experimental results show that the bistability triggering force can be tuned between 0.5 and 5.0 N. Incorporating this bistable actuator, the first group of hierarchical designs demonstrate the deployment of space frame structures with a tetrahedron module consisting of three active edges, each containing four serially connected actuators. The second group shows the design of flat structures that assume either positive or negative Gaussian curvature once activated. By flipping the initial configuration of the unit actuators, structures such as a dome and an enclosure are demonstrated. A modified Dynamic Relaxation method is used to simulate all possible geometries of the hierarchical structures. Measured geometries differ by less than 5% compared to simulation results. PMID:28361891

Statistical shear lag model - unraveling the size effect in hierarchical composites.

PubMed

Wei, Xiaoding; Filleter, Tobin; Espinosa, Horacio D

2015-05-01

Numerous experimental and computational studies have established that the hierarchical structures encountered in natural materials, such as the brick-and-mortar structure observed in sea shells, are essential for achieving defect tolerance. Due to this hierarchy, the mechanical properties of natural materials have a different size dependence compared to that of typical engineered materials. This study aimed to explore size effects on the strength of bio-inspired staggered hierarchical composites and to define the influence of the geometry of constituents in their outstanding defect tolerance capability. A statistical shear lag model is derived by extending the classical shear lag model to account for the statistics of the constituents' strength. A general solution emerges from rigorous mathematical derivations, unifying the various empirical formulations for the fundamental link length used in previous statistical models. The model shows that the staggered arrangement of constituents grants composites a unique size effect on mechanical strength in contrast to homogenous continuous materials. The model is applied to hierarchical yarns consisting of double-walled carbon nanotube bundles to assess its predictive capabilities for novel synthetic materials. Interestingly, the model predicts that yarn gauge length does not significantly influence the yarn strength, in close agreement with experimental observations. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Methanesulfonic acid-assisted synthesis of N/S co-doped hierarchically porous carbon for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Huo, Silu; Liu, Mingquan; Wu, Linlin; Liu, Mingjie; Xu, Min; Ni, Wei; Yan, Yi-Ming

2018-05-01

Nitrogen and sulfur co-doped carbons are considered as electrode materials for high performance supercapacitors, while their further development is still limited by complicated synthesis procedure, unsatisfied structure and low energy density. Developing a simple synthetic strategy to obtain rationally structured carbon materials and high supercapacitor performance is remaining a grand challenge. Herein, we describe the synthesis of nitrogen and sulfur co-doped hierarchical porous carbons as high performance supercapacitors electrode by a methanesulfonic acid-assisted one-step carbonization and activation of the freeze-dried precursors mixture. The as-prepared carbon material not only exhibits ideally hierarchical pores, but also realizes uniform nitrogen and sulfur co-doping. In 6.0 M KOH electrolyte, the material can achieve a high specific capacitance of 272 F g-1 at 1.0 A g-1 and a promising rate performance retaining 172 F g-1 even at 100 A g-1. Moreover, a fabricated symmetric supercapacitor based on as-prepared nitrogen and sulfur co-doped hierarchical porous carbon delivers high energy densities of 12.4 W h kg-1 and 8.0 W h kg-1 in 6.0 M KOH liquid and KOH/PVA solid-state electrolytes, respectively. This work presents a simple and effective methanesulfonic acid-assisted approach for mass production of heteroatomic doping hierarchical porous carbons for future energy storage applications.

Synthesis of uniform layered protonated titanate hierarchical spheres and their transformation to anatase TiO2 for lithium-ion batteries.

PubMed

Wu, Hao Bin; Lou, Xiong Wen David; Hng, Huey Hoon

2012-02-13

Layered protonated titanates (LPTs), a class of interesting inorganic layered materials, have been widely studied because of their many unique properties and their use as precursors to many important TiO(2)-based functional materials. In this work, we have developed a facile solvothermal method to synthesize hierarchical spheres (HSs) assembled from ultrathin LPT nanosheets. These LPT hierarchical spheres possess a porous structure with a large specific surface area and high stability. Importantly, the size and morphology of the LPT hierarchical spheres are easily tunable by varying the synthesis conditions. These LPT HSs can be easily converted to anatase TiO(2) HSs without significant structural alteration. Depending on the calcination atmosphere of air or N(2), pure anatase TiO(2) HSs or carbon-supported TiO(2) HSs, respectively, can be obtained. Remarkably, both types of TiO(2) HSs manifest excellent cyclability and rate capability when evaluated as anode materials for high-power lithium-ion batteries. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of catalyst pore structure and acid properties on the dehydration of glycerol.

PubMed

Choi, Youngbo; Park, Hongseok; Yun, Yang Sik; Yi, Jongheop

2015-03-01

Hierarchical porous catalysts have recently attracted increasing interest because of the enhanced accessibility to active sites on such materials. In this context, previously reported hierarchically mesoporous ASN and ASPN materials are evaluated by applying them to the dehydration of glycerol, and demonstrate excellent catalytic performance. In addition, a comprehensive understanding of the effects of pore structures and the acid properties on the reaction through comparative studies with microporous HZSM-5 and mesoporous AlMCM-41 is provided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward Scalable Fabrication of Hierarchical Silica Capsules with Integrated Micro-, Meso-, and Macropores.

PubMed

Zhou, Weizheng; Tong, Gangsheng; Wang, Dali; Zhu, Bangshang; Ren, Yu; Butler, Michael; Pelan, Eddie; Yan, Deyue; Zhu, Xinyuan; Stoyanov, Simeon D

2016-04-06

Hierarchical porous structures are ubiquitous in biological organisms and inorganic systems. Although such structures have been replicated, designed, and fabricated, they are often inferior to naturally occurring analogues. Apart from the complexity and multiple functionalities developed by the biological systems, the controllable and scalable production of hierarchically porous structures and building blocks remains a technological challenge. Herein, a facile and scalable approach is developed to fabricate hierarchical hollow spheres with integrated micro-, meso-, and macropores ranging from 1 nm to 100 μm (spanning five orders of magnitude). (Macro)molecules, micro-rods (which play a key role for the creation of robust capsules), and emulsion droplets have been successfully employed as multiple length scale templates, allowing the creation of hierarchical porous macrospheres. Thanks to their specific mechanical strength, these hierarchical porous spheres could be incorporated and assembled as higher level building blocks in various novel materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and condensation characteristics of metallic superhydrophobic surface with hierarchical micro-nano structures

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Wu, Xiaomin

2016-05-01

Metallic superhydrophobic surfaces have various applications in aerospace, refrigeration and other engineering fields due to their excellent water repellent characteristics. This study considers a simple but widely applicable fabrication method using a two simultaneous chemical reactions method to prepare the acid-salt mixed solutions to process the metal surfaces with surface deposition and surface etching to construct hierarchical micro-nano structures on the surface and then modify the surface with low surface-energy materials. Al-based and Cu-based superhydrophobic surfaces were fabricated using this method. The Al-based superhydrophobic surface had a water contact angle of 164° with hierarchical micro-nano structures similar to the lotus leaves. The Cu-based surface had a water contact angle of 157° with moss-like hierarchical micro-nano structures. Droplet condensation experiments were also performed on these two superhydrophobic surfaces to investigate their condensation characteristics. The results show that the Al-based superhydrophobic surface has lower droplet density, higher droplet jumping probability, slower droplet growth rate and lower surface coverage due to the more structured hierarchical structures.

Distinct Photovoltaic Performance of Hierarchical Nanostructures Self-Assembled from Multiblock Copolymers.

PubMed

Xu, Zhanwen; Lin, Jiaping; Zhang, Liangshun; Wang, Liquan; Wang, Gengchao; Tian, Xiaohui; Jiang, Tao

2018-06-14

We applied a multi-scale approach coupling dissipative particle dynamics method with a drift-diffusion model to elucidate the photovoltaic properties of multiblock copolymers consisting of alternating electron donor and acceptor blocks. A series of hierarchical lamellae-in-lamellar structures were obtained from the self-assembly of the multiblock copolymers. A distinct improvement in photovoltaic performance upon the morphology transformation from lamella to lamellae-in-lamella was observed. The hierarchical lamellae-in-lamellar structures significantly enhanced exciton dissociation and charge carrier transport, which consequently contributed to the improved photovoltaic performance. Based on our theoretical calculations, the hierarchical nanostructures can achieve a much enhanced energy conversion efficiency, improved by around 25% compared with that of general ones, through structure modulation on number and size of the small-length-scale domains. Our findings are supported by recent experimental evidence and yield guidelines for designing hierarchical materials with improved photovoltaic properties.

Supramolecular structure of polymer binders and composites: targeted control based on the hierarchy

NASA Astrophysics Data System (ADS)

Matveeva, Larisa; Belentsov, Yuri

2017-10-01

The article discusses the problem of targeted control over properties by modifying the supramolecular structure of polymer binders and composites based on their hierarchy. Control over the structure formation of polymers and introduction of modifying additives should be tailored to the specific hierarchical structural levels. Characteristics of polymer materials are associated with structural defects, which also display a hierarchical pattern. Classification of structural defects in polymers is presented. The primary structural level (nano level) of supramolecular formations is of great importance to the reinforcement and regulation of strength characteristics.

3D printed hierarchical honeycombs with shape integrity under large compressive deformations

DOE PAGES

Chen, Yanyu; Li, Tiantian; Jia, Zian; ...

2017-10-12

Here, we describe the in-plane compressive performance of a new type of hierarchical cellular structure created by replacing cell walls in regular honeycombs with triangular lattice configurations. The fabrication of this relatively complex material architecture with size features spanning from micrometer to centimeter is facilitated by the availability of commercial 3D printers. We apply to these hierarchical honeycombs a thermal treatment that facilitates the shape preservation and structural integrity of the structures under large compressive loading. The proposed hierarchical honeycombs exhibit a progressive failure mode, along with improved stiffness and energy absorption under uniaxial compression. High energy dissipation and shapemore » integrity at large imposed strains (up to 60%) have also been observed in these hierarchical honeycombs under cyclic loading. Experimental and numerical studies suggest that these anomalous mechanical behaviors are attributed to the introduction of a structural hierarchy, intrinsically controlled by the cell wall slenderness of the triangular lattice and by the shape memory effect induced by the thermal and mechanical compressive treatment.« less

3D printed hierarchical honeycombs with shape integrity under large compressive deformations

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

Chen, Yanyu; Li, Tiantian; Jia, Zian

Here, we describe the in-plane compressive performance of a new type of hierarchical cellular structure created by replacing cell walls in regular honeycombs with triangular lattice configurations. The fabrication of this relatively complex material architecture with size features spanning from micrometer to centimeter is facilitated by the availability of commercial 3D printers. We apply to these hierarchical honeycombs a thermal treatment that facilitates the shape preservation and structural integrity of the structures under large compressive loading. The proposed hierarchical honeycombs exhibit a progressive failure mode, along with improved stiffness and energy absorption under uniaxial compression. High energy dissipation and shapemore » integrity at large imposed strains (up to 60%) have also been observed in these hierarchical honeycombs under cyclic loading. Experimental and numerical studies suggest that these anomalous mechanical behaviors are attributed to the introduction of a structural hierarchy, intrinsically controlled by the cell wall slenderness of the triangular lattice and by the shape memory effect induced by the thermal and mechanical compressive treatment.« less

Structural hierarchies define toughness and defect-tolerance despite simple and mechanically inferior brittle building blocks

NASA Astrophysics Data System (ADS)

Sen, Dipanjan; Buehler, Markus J.

2011-07-01

Mineralized biological materials such as bone, sea sponges or diatoms provide load-bearing and armor functions and universally feature structural hierarchies from nano to macro. Here we report a systematic investigation of the effect of hierarchical structures on toughness and defect-tolerance based on a single and mechanically inferior brittle base material, silica, using a bottom-up approach rooted in atomistic modeling. Our analysis reveals drastic changes in the material crack-propagation resistance (R-curve) solely due to the introduction of hierarchical structures that also result in a vastly increased toughness and defect-tolerance, enabling stable crack propagation over an extensive range of crack sizes. Over a range of up to four hierarchy levels, we find an exponential increase in the defect-tolerance approaching hundred micrometers without introducing additional mechanisms or materials. This presents a significant departure from the defect-tolerance of the base material, silica, which is brittle and highly sensitive even to extremely small nanometer-scale defects.

Hierarchical porous carbon materials prepared using nano-ZnO as a template and activation agent for ultrahigh power supercapacitors.

PubMed

Wang, Haoran; Yu, Shukai; Xu, Bin

2016-09-20

Hierarchical porous carbon materials with high surface areas and a localized graphitic structure were simply prepared from sucrose using nano-ZnO as a hard template, activation agent and graphitization catalyst simultaneously, which exhibit an outstanding high-rate performance and can endure an ultrafast scan rate of 20 V s -1 and ultrahigh current density of 1000 A g -1 .

Correlation between the hierarchical structures and nanomechanical properties of amyloid fibrils.

PubMed

Lee, Gyudo; Lee, Wonseok; Baik, Seunghyun; Kim, Yong Ho; Eom, Kilho; Kwon, Taeyun

2018-04-12

Amyloid fibrils have recently been highlighted due to their excellent mechanical properties, which not only play a role in their biological functions but also imply their applications in biomimetic material design. Despite recent efforts to unveil how the excellent mechanical properties of amyloid fibrils originate, it has remained elusive how the anisotropic nanomechanical properties of hierarchically structured amyloid fibrils are determined. Here, we characterize the anisotropic nanomechanical properties of hierarchically structured amyloid fibrils using atomic force microscopy (AFM) experiments and atomistic simulations. It is shown that the hierarchical structure of amyloid fibrils plays a crucial role in determining their radial elastic property but does not make any effect on their radial bending elastic property. This is attributed to the role of intermolecular force acting between the filaments (constituting the fibril) on the radial elastic modulus of amyloid fibrils. Our finding illustrates how the hierarchical structure of amyloid fibrils encodes their anisotropic nanomechanical properties. Our study provides key design principles of amyloid fibrils, which endow valuable insight into the underlying mechanisms of amyloid mechanics. © 2018 IOP Publishing Ltd.

DNA Architectures for Templated Material Growth

DTIC Science & Technology

2011-09-01

Solubilization of the DNA in non-aqueous solvents is achieved by replacing charge stabilizing salts with surfactants. Retention of DNA hierarchical structure...solvents is achieved by replacing charge stabilizing salts with surfactants. Retention of DNA hierarchical structure under both conditions will be...studied and explained, and is only being reproduced in this experiment.12-14 Both CTAB and CTAC, were reacted with the reconstituted DNA (salmon sperm

Hierarchical porous carbon aerogel derived from bagasse for high performance supercapacitor electrode.

PubMed

Hao, Pin; Zhao, Zhenhuan; Tian, Jian; Li, Haidong; Sang, Yuanhua; Yu, Guangwei; Cai, Huaqiang; Liu, Hong; Wong, C P; Umar, Ahmad

2014-10-21

Renewable, cost-effective and eco-friendly electrode materials have attracted much attention in the energy conversion and storage fields. Bagasse, the waste product from sugarcane that mainly contains cellulose derivatives, can be a promising candidate to manufacture supercapacitor electrode materials. This study demonstrates the fabrication and characterization of highly porous carbon aerogels by using bagasse as a raw material. Macro and mesoporous carbon was first prepared by carbonizing the freeze-dried bagasse aerogel; consequently, microporous structure was created on the walls of the mesoporous carbon by chemical activation. Interestingly, it was observed that the specific surface area, the pore size and distribution of the hierarchical porous carbon were affected by the activation temperature. In order to evaluate the ability of the hierarchical porous carbon towards the supercapacitor electrode performance, solid state symmetric supercapacitors were assembled, and a comparable high specific capacitance of 142.1 F g(-1) at a discharge current density of 0.5 A g(-1) was demonstrated. The fabricated solid state supercapacitor displayed excellent capacitance retention of 93.9% over 5000 cycles. The high energy storage ability of the hierarchical porous carbon was attributed to the specially designed pore structures, i.e., co-existence of the micropores and mesopores. This research has demonstrated that utilization of sustainable biopolymers as the raw materials for high performance supercapacitor electrode materials is an effective way to fabricate low-cost energy storage devices.

Multiscale Inorganic Hierarchically Materials: Towards an Improved Orthopaedic Regenerative Medicine.

PubMed

Ruso, Juan M; Sartuqui, Javier; Messina, Paula V

2015-01-01

Bone is a biologically and structurally sophisticated multifunctional tissue. It dynamically responds to biochemical, mechanical and electrical clues by remodelling itself and accordingly the maximum strength and toughness are along the lines of the greatest applied stress. The challenge is to develop an orthopaedic biomaterial that imitates the micro- and nano-structural elements and compositions of bone to locally match the properties of the host tissue resulting in a biologically fixed implant. Looking for the ideal implant, the convergence of life and materials sciences occurs. Researchers in many different fields apply their expertise to improve implantable devices and regenerative medicine. Materials of all kinds, but especially hierarchical nano-materials, are being exploited. The application of nano-materials with hierarchical design to calcified tissue reconstructive medicine involve intricate systems including scaffolds with multifaceted shapes that provides temporary mechanical function; materials with nano-topography modifications that guarantee their integration to tissues and that possesses functionalized surfaces to transport biologic factors to stimulate tissue growth in a controlled, safe, and rapid manner. Furthermore materials that should degrade on a timeline coordinated to the time that takes the tissues regrow, are prepared. These implantable devices are multifunctional and for its construction they involve the use of precise strategically techniques together with specific material manufacturing processes that can be integrated to achieve in the design, the required multifunctionality. For such reasons, even though the idea of displacement from synthetic implants and tissue grafts to regenerative-medicine-based tissue reconstruction has been guaranteed for well over a decade, the reality has yet to emerge. In this paper, we examine the recent approaches to create enhanced bioactive materials. Their design and manufacturing procedures as well as the experiments to integrate them into engineer hierarchical inorganic materials for their practical application in calcified tissue reparation are evaluated.

Exploring the significance of structural hierarchy in material systems-A review

NASA Astrophysics Data System (ADS)

Pan, Ning

2014-06-01

Structural hierarchy and heterogeneity are inherent features in biological materials, but their significance in affecting the system behaviors is yet to be fully understood. In Sec. I, this article first identifies the major characteristics that manifest, or are resulted from, such hierarchy and heterogeneity in materials. Then in Sec. II, it presents several typical natural material systems including wood, bone, and others from animals to illustrate the proposed views. The paper also discusses a man-made smart material, textiles, to demonstrate that textiles are hierarchal, multifunctional, highly complex, and arguably the engineered material closest on a par with biological materials in complexity, and, more importantly, we can still learn quite a few new things from them in development of novel materials. In Sec. III, the paper summarizes several general approaches in developing a hierarchal material system at various scales, including structure thinning and splitting, laminating and layering, spatial and angular orientation, heterogenization and hybridization, and analyzes the advantages associated with them. It also stresses the adverse consequences once the existing structural hierarchy breaks down due to various mutations in biological systems. It discusses, in particular, the influences of moisture and air on material properties, given the near ubiquitousness of both air and water in materials. It next deals with in Sec. IV, some theoretical issues in material research including packing and ordering, the bi-modular mechanics, the behavior non-affinities due to disparity in hierarchal levels, the importance of system dimensionality in a hierarchal material system, and more philosophically, the issues of Nature's wisdom versus Intelligent Design. Section V then offers some concluding remarks, including a recap of the major issues covered in this article, and some general conclusions derived from the analyses and discussions. The main purpose of this paper is to make an effort to explore, identify, derive, or theorize some generic principles based on the existing results, not to offer another comprehensive review of current research activities in the fields for that there already exist some excellent ones. This paper examines the related topics with several approaches to not only reveal the underlying geometrical and physical mechanisms but also to emphasize the ways in which such mechanisms may be applied to developing engineered material systems with novel properties.

Hierarchical porous carbon microspheres derived from porous starch for use in high-rate electrochemical double-layer capacitors.

PubMed

Du, Si-Hong; Wang, Li-Qun; Fu, Xiao-Ting; Chen, Ming-Ming; Wang, Cheng-Yang

2013-07-01

Porous starch was used as a precursor for hierarchical porous carbon microspheres. The preparation consisted of stabilisation, carbonisation and KOH activation, and the resultant hierarchical porous carbon microspheres had a large BET surface area of 3251 m(2)g(-1). Due to the large surface area and the hierarchical pore structure, electrodes made of the hierarchical porous carbon microsphere materials had high specific capacitances of 304 Fg(-1) at a current density of 0.05 Ag(-1) and 197 Fg(-1) at a current density of 180 Ag(-1) when used in a symmetric capacitor with 6M KOH as the electrolyte. After 10,000 cycles, the capacitor still exhibited a stable performance with a capacitance retention of 98%. These results indicate that porous starch is an excellent precursor to prepare high performance electrode materials for EDLCs. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hierarchical Micro-/Nanostructures from Human Hair for Biomedical Applications.

PubMed

Zheng, Di-Wei; Hong, Sheng; Xu, Lu; Li, Chu-Xin; Li, Ke; Cheng, Si-Xue; Zhang, Xian-Zheng

2018-05-21

With the prominent progress of biomedical engineering, materials with high biocompatibility and versatile functions are urgently needed. So far, hierarchical structures in nature have shed some light on the design of high performance materials both in concept and implementation. Inspired by these, the hierarchical micro-/nanostructures of human hair are explored and human hair is further broken into hierarchical microparticles (HMP) and hierarchical nanoparticles (HNP) with top-down procedures. Compared with commercialized carriers, such as liposomes or albumin nanoparticles, the obtained particles exhibit high hemocompatibility and negligible immunogenicity. Furthermore, these materials also display attentional abilities in the aspects of light absorption and free radical scavenging. It is found that HMP and HNP can prevent skin from UV-induced damage and relieve symptoms of cataract in vitro. Besides, both HMP and HNP show satisfactory photothermal conversion ability. By using microcomputed tomography and intravital fluorescence microscopy, it is found that warfarin-loaded HMP can rescue mice from vein thrombosis. In another aspect, HNP modified with tumor targeted aptamers exhibit dramatic antineoplastic effect, and suppress 96.8% of tumor growth in vivo. Thus, the multifaceted materials described here might provide a new tool for addressing biomedical challenges. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical NiCo2 S4 Nanotube@NiCo2 S4 Nanosheet Arrays on Ni Foam for High-Performance Supercapacitors.

PubMed

Chen, Haichao; Chen, Si; Shao, Hongyan; Li, Chao; Fan, Meiqiang; Chen, Da; Tian, Guanglei; Shu, Kangying

2016-01-01

Hierarchical NiCo2 S4 nanotube@NiCo2 S4 nanosheet arrays on Ni foam have been successfully synthesized. Owing to the unique hierarchical structure, enhanced capacitive performance can be attained. A specific capacitance up to 4.38 F cm(-2) is attained at 5 mA cm(-2) , which is much higher than the specific capacitance values of NiCo2 O4 nanosheet arrays, NiCo2 S4 nanosheet arrays and NiCo2 S4 nanotube arrays on Ni foam. The hierarchical NiCo2 S4 nanostructure shows superior cycling stability; after 5000 cycles, the specific capacitance still maintains 3.5 F cm(-2) . In addition, through the morphology and crystal structure measurement after cycling stability test, it is found that the NiCo2 S4 electroactive materials are gradually corroded; however, the NiCo2 S4 phase can still be well-maintained. Our results show that hierarchical NiCo2 S4 nanostructures are suitable electroactive materials for high performance supercapacitors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of hierarchical porous N-doping carbon membrane by using ;confined nanospace deposition; method for supercapacitor

NASA Astrophysics Data System (ADS)

Wang, Guoxu; Liu, Meng; Du, Juan; Liu, Lei; Yu, Yifeng; Sha, Jitong; Chen, Aibing

2018-03-01

The membrane carbon materials with hierarchical porous architecture are attractive because they can provide more channels for ion transport and shorten the ions transport path. Herein, we develop a facile way based on "confined nanospace deposition" to fabricate N-dopi-ng three dimensional hierarchical porous membrane carbon material (N-THPMC) via coating the nickel nitrate, silicate oligomers and triblock copolymer P123 on the branches of commercial polyamide membrane (PAM). During high temperature treatment, the mesoporous silica layer and Ni species serve as a "confined nanospace" and catalyst respectively, which are indispensable elements for formation of carbon framework, and the gas-phase carbon precursors which derive from the decomposition of PAM are deposited into the "confined nanospace" forming carbon framework. The N-THPMC with hierarchical macro/meso/microporous structure, N-doping (2.9%) and large specific surface area (994m2 g-1) well inherits the membrane morphology and hierarchical porous structure of PAM. The N-THPMC as electrode without binder exhibits a specific capacitance of 252 F g-1 at the current density of 1 A g-1 in 6 M KOH electrolyte and excellent cycling stability of 92.7% even after 5000 cycles.

Microparticles with hierarchical porosity

DOEpatents

Petsev, Dimiter N; Atanassov, Plamen; Pylypenko, Svitlana; Carroll, Nick; Olson, Tim

2012-12-18

The present disclosure provides oxide microparticles with engineered hierarchical porosity and methods of manufacturing the same. Also described are structures that are formed by templating, impregnating, and/or precipitating the oxide microparticles and method for forming the same. Suitable applications include catalysts, electrocatalysts, electrocatalysts support materials, capacitors, drug delivery systems, sensors and chromatography.

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

DOE PAGES

Lin, Feng; Xin, Huolin L.; Nordlund, Dennis; ...

2016-01-11

Controlling surface and interfacial properties of battery materials is key to improving performance in rechargeable Li-ion devices. Surface reconstruction from a layered to a rock salt structure in metal oxide cathode materials is commonly observed and results in poor high-voltage cycling performance, impeding attempts to improve energy density. Hierarchically structured LiNi 0.4Mn 0.4Co 0.2O 2 (NMC-442) spherical powders, made by spray pyrolysis, exhibit local elemental distribution gradients that deviate from the global NMC-442 composition; specifically, they are Ni-rich and Mn-poor at particle surfaces. These materials demonstrate improved Coulombic efficiencies, discharge capacities, and high-voltage capacity retention in lithium half-cell configurations. Themore » subject powders show superior resistance against surface reconstruction due to the tailored surface chemistry, compared to conventional NMC-442 materials. This paves the way towards the development of a new generation of robust and stable high-energy NMC cathodes for Li-ion batteries.« less

Assembly of Layered Monetite-Chitosan Nanocomposite and Its Transition to Organized Hydroxyapatite.

PubMed

Ruan, Qichao; Liberman, David; Zhang, Yuzheng; Ren, Dongni; Zhang, Yunpeng; Nutt, Steven; Moradian-Oldak, Janet

2016-06-13

Bioinspired synthesis of hierarchically structured calcium phosphate (CaP) material is a highly promising strategy for developing improved bone substitute materials. However, synthesis of CaP materials with outstanding mechanical properties still remains an ongoing challenge. Inspired by the formation of lamellar structure in nacre, we designed an organic matrix composed of chitosan and cis-butenediolic acid (maleic acid, MAc) that could assemble into a layered complex and further guide the mineralization of monetite crystals, resulting in the formation of organized and parallel arrays of monetite platelets with a brick-and-mortar structure. Using the layered monetite-chitosan composite as a precursor, we were able to synthesize hydroxyapatite (HAp) with multiscale hierarchically ordered structure via a topotactic phase transformation process. On the nanoscale, needlelike HAp crystallites assembled into organized bundles that aligned to form highly oriented plates on the microscale. On the large-scale level, these plates with different crystal orientations were stacked together to form a layered structure. The organized structures and composite feature yielded CaP materials with improved mechanical properties close to those of bone. Our study introduces a biomimetic approach that may be practical for the design of advanced, mechanically robust materials for biomedical applications.

Biomimetic cellular metals-using hierarchical structuring for energy absorption.

PubMed

Bührig-Polaczek, A; Fleck, C; Speck, T; Schüler, P; Fischer, S F; Caliaro, M; Thielen, M

2016-07-19

Fruit walls as well as nut and seed shells typically perform a multitude of functions. One of the biologically most important functions consists in the direct or indirect protection of the seeds from mechanical damage or other negative environmental influences. This qualifies such biological structures as role models for the development of new materials and components that protect commodities and/or persons from damage caused for example by impacts due to rough handling or crashes. We were able to show how the mechanical properties of metal foam based components can be improved by altering their structure on various hierarchical levels inspired by features and principles important for the impact and/or puncture resistance of the biological role models, rather than by tuning the properties of the bulk material. For this various investigation methods have been established which combine mechanical testing with different imaging methods, as well as with in situ and ex situ mechanical testing methods. Different structural hierarchies especially important for the mechanical deformation and failure behaviour of the biological role models, pomelo fruit (Citrus maxima) and Macadamia integrifolia, were identified. They were abstracted and transferred into corresponding structural principles and thus hierarchically structured bio-inspired metal foams have been designed. A production route for metal based bio-inspired structures by investment casting was successfully established. This allows the production of complex and reliable structures, by implementing and combining different hierarchical structural elements found in the biological concept generators, such as strut design and integration of fibres, as well as by minimising casting defects. To evaluate the structural effects, similar investigation methods and mechanical tests were applied to both the biological role models and the metallic foams. As a result an even deeper quantitative understanding of the form-structure-function relationship of the biological concept generators as well as the bio-inspired metal foams was achieved, on deeper hierarchical levels and overarching different levels.

Hierarchically Self-Assembled Star-Shaped ZnO Microparticles for Electrochemical Sensing of Amines.

PubMed

Du, Jianping; Huang, Xiaoxi; Zhao, Ruihua; Li, Jinping; Asefa, Tewodros

2016-06-06

Novel, hierarchically nanostructured, star-shaped ZnO (SSZ) microparticles are synthesized by a hydrothermal synthetic route. The SSZ microparticles serve as effective platforms for electrochemical detection of amines in solution. The morphology and structure of the materials are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and UV/Vis spectroscopy. The as-synthesized SSZ microparticles comprise self-assembled hexagonal prisms that possess nanometer and micrometer pores in their structure and on their surfaces-structural features that are conducive to sensing applications. An electrode fabricated by using the hierarchically nanostructured SSZ materials serve as a sensitive electrochemical sensor for detection of low concentrations of ethylenediamine, with a sensitivity of 2.98×10(-2)  mA cm(-2)  mm(-1) , a detection limit of 2.36×10(-2)  mm, and a short response time of 8 s. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

PubMed

Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

2015-07-21

Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content.

Synergistic effects from graphene and carbon nanotubes endow ordered hierarchical structure foams with a combination of compressibility, super-elasticity and stability and potential application as pressure sensors

NASA Astrophysics Data System (ADS)

Kuang, Jun; Dai, Zhaohe; Liu, Luqi; Yang, Zhou; Jin, Ming; Zhang, Zhong

2015-05-01

Nanostructured carbon material based three-dimensional porous architectures have been increasingly developed for various applications, e.g. sensors, elastomer conductors, and energy storage devices. Maintaining architectures with good mechanical performance, including elasticity, load-bearing capacity, fatigue resistance and mechanical stability, is prerequisite for realizing these functions. Though graphene and CNT offer opportunities as nanoscale building blocks, it still remains a great challenge to achieve good mechanical performance in their microarchitectures because of the need to precisely control the structure at different scales. Herein, we fabricate a hierarchical honeycomb-like structured hybrid foam based on both graphene and CNT. The resulting materials possess excellent properties of combined high specific strength, elasticity and mechanical stability, which cannot be achieved in neat CNT and graphene foams. The improved mechanical properties are attributed to the synergistic-effect-induced highly organized, multi-scaled hierarchical architectures. Moreover, with their excellent electrical conductivity, we demonstrated that the hybrid foams could be used as pressure sensors in the fields related to artificial skin.Nanostructured carbon material based three-dimensional porous architectures have been increasingly developed for various applications, e.g. sensors, elastomer conductors, and energy storage devices. Maintaining architectures with good mechanical performance, including elasticity, load-bearing capacity, fatigue resistance and mechanical stability, is prerequisite for realizing these functions. Though graphene and CNT offer opportunities as nanoscale building blocks, it still remains a great challenge to achieve good mechanical performance in their microarchitectures because of the need to precisely control the structure at different scales. Herein, we fabricate a hierarchical honeycomb-like structured hybrid foam based on both graphene and CNT. The resulting materials possess excellent properties of combined high specific strength, elasticity and mechanical stability, which cannot be achieved in neat CNT and graphene foams. The improved mechanical properties are attributed to the synergistic-effect-induced highly organized, multi-scaled hierarchical architectures. Moreover, with their excellent electrical conductivity, we demonstrated that the hybrid foams could be used as pressure sensors in the fields related to artificial skin. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00841g

Materials taking a lesson from nature.

PubMed

Tian, Liangfei; Croisier, Emmanuel; Frauenrath, Holger

2013-01-01

Structural biomaterials with their often extraordinary properties and versatile functions are typically constructed from very limited sets of building blocks and types of supramolecular interactions. In this review we discuss how, inspired by nature's design principles for protein-based materials, oligopeptide-modified polymers can be used as a versatile toolbox to program nanostructure and hierarchical structure formation in synthetic materials.

Category Theoretic Analysis of Hierarchical Protein Materials and Social Networks

PubMed Central

Spivak, David I.; Giesa, Tristan; Wood, Elizabeth; Buehler, Markus J.

2011-01-01

Materials in biology span all the scales from Angstroms to meters and typically consist of complex hierarchical assemblies of simple building blocks. Here we describe an application of category theory to describe structural and resulting functional properties of biological protein materials by developing so-called ologs. An olog is like a “concept web” or “semantic network” except that it follows a rigorous mathematical formulation based on category theory. This key difference ensures that an olog is unambiguous, highly adaptable to evolution and change, and suitable for sharing concepts with other olog. We consider simple cases of beta-helical and amyloid-like protein filaments subjected to axial extension and develop an olog representation of their structural and resulting mechanical properties. We also construct a representation of a social network in which people send text-messages to their nearest neighbors and act as a team to perform a task. We show that the olog for the protein and the olog for the social network feature identical category-theoretic representations, and we proceed to precisely explicate the analogy or isomorphism between them. The examples presented here demonstrate that the intrinsic nature of a complex system, which in particular includes a precise relationship between structure and function at different hierarchical levels, can be effectively represented by an olog. This, in turn, allows for comparative studies between disparate materials or fields of application, and results in novel approaches to derive functionality in the design of de novo hierarchical systems. We discuss opportunities and challenges associated with the description of complex biological materials by using ologs as a powerful tool for analysis and design in the context of materiomics, and we present the potential impact of this approach for engineering, life sciences, and medicine. PMID:21931622

Hierarchically porous silicon–carbon–nitrogen hybrid materials towards highly efficient and selective adsorption of organic dyes

PubMed Central

Meng, Lala; Zhang, Xiaofei; Tang, Yusheng; Su, Kehe; Kong, Jie

2015-01-01

The hierarchically macro/micro-porous silicon–carbon–nitrogen (Si–C–N) hybrid material was presented with novel functionalities of totally selective and highly efficient adsorption for organic dyes. The hybrid material was conveniently generated by the pyrolysis of commercial polysilazane precursors using polydivinylbenzene microspheres as sacrificial templates. Owing to the Van der Waals force between sp2-hybridized carbon domains and triphenyl structure of dyes, and electrostatic interaction between dyes and Si-C-N matrix, it exhibites high adsorption capacity and good regeneration and recycling ability for the dyes with triphenyl structure, such as methyl blue (MB), acid fuchsin (AF), basic fuchsin and malachite green. The adsorption process is determined by both surface adsorption and intraparticle diffusion. According to the Langmuir model, the adsorption capacity is 1327.7 mg·g−1 and 1084.5 mg·g−1 for MB and AF, respectively, which is much higher than that of many other adsorbents. On the contrary, the hybrid materials do not adsorb the dyes with azo benzene structures, such as methyl orange, methyl red and congro red. Thus, the hierarchically porous Si–C–N hybrid material from a facile and low cost polymer-derived strategy provides a new perspective and possesses a significant potential in the treatment of wastewater with complex organic pollutants. PMID:25604334

Two-Dimensional Porous Carbon: Synthesis and Ion-Transport Properties.

PubMed

Zheng, Xiaoyu; Luo, Jiayan; Lv, Wei; Wang, Da-Wei; Yang, Quan-Hong

2015-09-23

Their chemical stability, high specific surface area, and electric conductivity enable porous carbon materials to be the most commonly used electrode materials for electrochemical capacitors (also known as supercapacitors). To further increase the energy and power density, engineering of the pore structures with a higher electrochemical accessible surface area, faster ion-transport path and a more-robust interface with the electrolyte is widely investigated. Compared with traditional porous carbons, two-dimensional (2D) porous carbon sheets with an interlinked hierarchical porous structure are a good candidate for supercapacitors due to their advantages in high aspect ratio for electrode packing and electron transport, hierarchical pore structures for ion transport, and short ion-transport length. Recent progress on the synthesis of 2D porous carbons is reported here, along with the improved electrochemical behavior due to enhanced ion transport. Challenges for the controlled preparation of 2D porous carbons with desired properties are also discussed; these require precise tuning of the hierarchical structure and a clarification of the formation mechanisms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Emerging Hierarchical Aerogels: Self-Assembly of Metal and Semiconductor Nanocrystals.

PubMed

Cai, Bin; Sayevich, Vladimir; Gaponik, Nikolai; Eychmüller, Alexander

2018-06-19

Aerogels assembled from colloidal metal or semiconductor nanocrystals (NCs) feature large surface area, ultralow density, and high porosity, thus rendering them attractive in various applications, such as catalysis, sensors, energy storage, and electronic devices. Morphological and structural modification of the aerogel backbones while maintaining the aerogel properties enables a second stage of the aerogel research, which is defined as hierarchical aerogels. Different from the conventional aerogels with nanowire-like backbones, those hierarchical aerogels are generally comprised of at least two levels of architectures, i.e., an interconnected porous structure on the macroscale and a specially designed configuration at local backbones at the nanoscale. This combination "locks in" the inherent properties of the NCs, so that the beneficial genes obtained by nanoengineering are retained in the resulting monolithic hierarchical aerogels. Herein, groundbreaking advances in the design, synthesis, and physicochemical properties of the hierarchical aerogels are reviewed and organized in three sections: i) pure metallic hierarchical aerogels, ii) semiconductor hierarchical aerogels, and iii) metal/semiconductor hybrid hierarchical aerogels. This report aims to define and demonstrate the concept, potential, and challenges of the hierarchical aerogels, thereby providing a perspective on the further development of these materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biotemplated materials for sustainable energy and environment: current status and challenges.

PubMed

Zhou, Han; Fan, Tongxiang; Zhang, Di

2011-10-17

Materials science will play a key role in the further development of emerging solutions for the increasing problems of energy and environment. Materials found in nature have many inspiring structures, such as hierarchical organizations, periodic architectures, or nanostructures, that endow them with amazing functions, such as energy harvesting and conversion, antireflection, structural coloration, superhydrophobicity, and biological self-assembly. Biotemplating is an effective strategy to obtain morphology-controllable materials with structural specificity, complexity, and related unique functions. Herein, we highlight the synthesis and application of biotemplated materials for six key areas of energy and environment technologies, namely, photocatalytic hydrogen evolution, CO(2) reduction, solar cells, lithium-ion batteries, photocatalytic degradation, and gas/vapor sensing. Although the applications differ from each other, a common fundamental challenge is to realize optimum structures for improved performances. We highlight the role of four typical structures derived from biological systems exploited to optimize properties: hierarchical (porous) structures, periodic (porous) structures, hollow structures, and nanostructures. We also provide examples of using biogenic elements (e.g., C, Si, N, I, P, S) for the creation of active materials. Finally, we disscuss the challenges of achieving the desired performance for large-scale commercial applications and provide some useful prototypes from nature for the biomimetic design of new materials or systems. The emphasis is mainly focused on the structural effects and compositional utilization of biotemplated materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pore-scale study of effects of macroscopic pores and their distributions on reactive transport in hierarchical porous media

DOE PAGES

Chen, Li; Zhang, Ruiyuan; Min, Ting; ...

2018-05-19

For applications of reactive transport in porous media, optimal porous structures should possess both high surface area for reactive sites loading and low mass transport resistance. Hierarchical porous media with a combination of pores at different scales are designed for this purpose. In this paper, using the lattice Boltzmann method, pore-scale numerical studies are conducted to investigate diffusion-reaction processes in 2D hierarchical porous media generated by self-developed reconstruction scheme. Complex interactions between porous structures and reactive transport are revealed under different conditions. Simulation results show that adding macropores can greatly enhance the mass transport, but at the same time reducemore » the reactive surface, leading to complex change trend of the total reaction rate. Effects of gradient distribution of macropores within the porous medium are also investigated. It is found that a front-loose, back-tight (FLBT) hierarchical structure is desirable for enhancing mass transport, increasing total reaction rate, and improving catalyst utilization. Finally, on the whole, from the viewpoint of reducing cost and improving material performance, hierarchical porous structures, especially gradient structures with the size of macropores gradually decreasing along the transport direction, are desirable for catalyst application.« less

Pore-scale study of effects of macroscopic pores and their distributions on reactive transport in hierarchical porous media

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

Chen, Li; Zhang, Ruiyuan; Min, Ting

For applications of reactive transport in porous media, optimal porous structures should possess both high surface area for reactive sites loading and low mass transport resistance. Hierarchical porous media with a combination of pores at different scales are designed for this purpose. In this paper, using the lattice Boltzmann method, pore-scale numerical studies are conducted to investigate diffusion-reaction processes in 2D hierarchical porous media generated by self-developed reconstruction scheme. Complex interactions between porous structures and reactive transport are revealed under different conditions. Simulation results show that adding macropores can greatly enhance the mass transport, but at the same time reducemore » the reactive surface, leading to complex change trend of the total reaction rate. Effects of gradient distribution of macropores within the porous medium are also investigated. It is found that a front-loose, back-tight (FLBT) hierarchical structure is desirable for enhancing mass transport, increasing total reaction rate, and improving catalyst utilization. Finally, on the whole, from the viewpoint of reducing cost and improving material performance, hierarchical porous structures, especially gradient structures with the size of macropores gradually decreasing along the transport direction, are desirable for catalyst application.« less

Spine-like Nanostructured Carbon Interconnected by Graphene for High-performance Supercapacitors

NASA Astrophysics Data System (ADS)

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-08-01

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp2 carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp2 carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance.

Spine-like nanostructured carbon interconnected by graphene for high-performance supercapacitors.

PubMed

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-08-19

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp(2) carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp(2) carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance.

Spine-like Nanostructured Carbon Interconnected by Graphene for High-performance Supercapacitors

PubMed Central

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-01-01

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp2 carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp2 carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance. PMID:25134517

Fabrication of hierarchical flower-like porous ZnO nanostructures from layered ZnC2O4·3Zn(OH)2 and gas sensing properties

NASA Astrophysics Data System (ADS)

Cui, Jiashan; Sun, Jianbo; Liu, Xin; Li, Jinwei; Ma, Xinzhi; Chen, Tingting

2014-07-01

ZnO materials with porous and hierarchical flower-like structure were synthesized through mild hydrothermal and simple calcination approach, in which the flower-like layered zinc oxalate hydroxide (ZnC2O4·3Zn(OH)2) precursor was first synthesized and then calcined at 600 °C. The obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopic (TEM), Brunauer-Emmett-Teller (BET) and thermogravimetric (TG) analysis. We proposed the possible growth mechanism of the material via studying the time evolution experiment results. In the process of reaction, oxalic acid as a structure-directing agent hydrolyzed and then formed primarily sheets-like intermediate ZnC2O4·2H2O. Hexamethylenetetramine (HMT) as surfactant, with directional adsorption, leads to the formation of layered zinc oxalate hydroxide precursor. Furthermore, the gas sensitivity also can be characterized, whose results indicated that the synthesized materials had a preferable selectivity to ethanol gas. The fast response rate and reversible performance can be attributed to the produced greater specific surface area produced, which was caused by the porous and hierarchical flower-like structure.

A review of terrestrial, aerial and aquatic keratins: the structure and mechanical properties of pangolin scales, feather shafts and baleen plates.

PubMed

Wang, Bin; Sullivan, Tarah N

2017-12-01

Keratinous materials, omnipresent as the hard and durable epidermal appendages of animals, are among the toughest biological materials. They exhibit diverse morphologies and structures that serve a variety of amazing and inspiring mechanical functions. In this work, we provide a review of representative terrestrial, aerial and aquatic keratinous materials, pangolin scales, feather shafts and baleen plates, and correlate their hierarchical structures to respective functions of dermal armor, flight material and undersea filter. The overlapping pattern of pangolin scales provides effective body coverage, and the solid scales show transverse isotropy and strain-rate sensitivity, both important for armor function. The feather shaft displays a distinct shape factor, hierarchical fibrous structure within the cortex, and a solid shell-over-foam design, which enables synergistic stiffening and toughening with exceptional lightness to fulfill flight. Baleen plates exhibit a sandwich-tubular structure that features anisotropic flexural properties to sustain forces from water flow and remarkable fracture toughness that ensures reliable undersea functioning. The latest findings regarding the structural design principles and mechanical properties are presented in order to advance current understanding of keratinous materials and to stimulate the development of new bioinspired materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxygen-rich hierarchical porous carbon derived from artemia cyst shells with superior electrochemical performance.

PubMed

Zhao, Yufeng; Ran, Wei; He, Jing; Song, Yanfang; Zhang, Chunming; Xiong, Ding-Bang; Gao, Faming; Wu, Jinsong; Xia, Yongyao

2015-01-21

In this study, three-dimensional (3D) hierarchical porous carbon with abundant functional groups is produced through a very simple low-cost carbonization of Artemia cyst shells. The unique hierarchical porous structure of this material, combining large numbers of micropores and macropores, as well as reasonable amount of mesopores, is proven favorable to capacitive behavior. The abundant oxygen functional groups from the natural carbon precursor contribute stable pseudocapacitance. As-prepared sample exhibits high specific capacitance (369 F g(-1) in 1 M H2SO4 and 349 F g(-1) in 6 M KOH), excellent cycling stability with capacitance retention of 100% over 10 000 cycles, and promising rate performance. This work not only describes a simple way to produce high-performance carbon electrode materials for practical application, but also inspires an idea for future structure design of porous carbon.

CoMn2O4 Spinel Hierarchical Microspheres Assembled with Porous Nanosheets as Stable Anodes for Lithium-ion Batteries

PubMed Central

Hu, Lin; Zhong, Hao; Zheng, Xinrui; Huang, Yimin; Zhang, Ping; Chen, Qianwang

2012-01-01

Herein, we report the feasibility to enhance the capacity and stability of CoMn2O4 anode materials by fabricating hierarchical mesoporous structure. The open space between neighboring nanosheets allows for easy diffusion of the electrolyte. The hierarchical microspheres assembled with nanosheets can ensure that every nanosheet participates in the electrochemical reaction, because every nanosheet is contacted with the electrolyte solution. The hierarchical structure and well interconnected pores on the surface of nanosheets will enhance the CoMn2O4/electrolyte contact area, shorten the Li+ ion diffusion length in the nanosheets, and accommodate the strain induced by the volume change during the electrochemical reaction. The last, hierarchical architecture with spherical morphology possesses relatively low surface energy, which results in less extent of self-aggregation during charge/discharge process. As a result, CoMn2O4 hierarchical microspheres can achieve a good cycle ability and high rate capability. PMID:23248749

Synthesis and electrochemical performance of polyaniline @MnO2/graphene ternary composites for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Pan, Chao; Gu, Haiteng; Dong, Li

2016-01-01

We introduce a facile method to construct new ternary hierarchical nanocomposites by combining MnO2 coated one dimensional (1D) conducting polyaniline (PANI) nanowires with 2D graphene sheets (GNs). The hierarchical nanocomposite structures of PANI@MnO2/GNs (PMGNs) are further proved by X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of the electrodes made of the hierarchical structured PMGNs materials are determined by the CV and galvanostatic measurements. These electrochemical tests indicate that electrodes made of the nanostructured PMGNs exhibit an improved reversible capacitance of 695 F g-1 after 1000 cycles at a high current density of 4 A g-1. The ternary composites possess higher electrochemical capacitance than each individual component as supercapacitor electrode materials. Such intriguing electrochemical performance is mainly attributed to the synergistic effects of MnO2, PANI and graphene. The hierarchical ternary nanocomposites show excellent electrochemical properties for energy storage applications, which evidence their potential application as supercapacitors.

Self-Reconstructed Formation of a One-Dimensional Hierarchical Porous Nanostructure Assembled by Ultrathin TiO2 Nanobelts for Fast and Stable Lithium Storage.

PubMed

Liu, Yuan; Yan, Xiaodong; Xu, Bingqing; Lan, Jinle; Yu, Yunhua; Yang, Xiaoping; Lin, Yuanhua; Nan, Cewen

2018-06-06

Owing to their unique structural advantages, TiO 2 hierarchical nanostructures assembled by low-dimensional (LD) building blocks have been extensively used in the energy-storage/-conversion field. However, it is still a big challenge to produce such advanced structures by current synthetic techniques because of the harsh conditions needed to generate primary LD subunits. Herein, a novel one-dimensional (1D) TiO 2 hierarchical porous fibrous nanostructure constructed by TiO 2 nanobelts is synthesized by combining a room-temperature aqueous solution growth mechanism with the electrospinning technology. The nanobelt-constructed 1D hierarchical nanoarchitecture is evolves directly from the amorphous TiO 2 /SiO 2 composite fibers in alkaline solutions at ambient conditions without any catalyst and other reactant. Benefiting from the unique structural features such as 1D nanoscale building blocks, large surface area, and numerous interconnected pores, as well as mixed phase anatase-TiO 2 (B), the optimum 1D TiO 2 hierarchical porous nanostructure shows a remarkable high-rate performance when tested as an anode material for lithium-ion batteries (107 mA h g -1 at ∼10 A g -1 ) and can be used in a hybrid lithium-ion supercapacitor with very stable lithium-storage performance (a capacity retention of ∼80% after 3000 cycles at 2 A g -1 ). The current work presents a scalable and cost-effective method for the synthesis of advanced TiO 2 hierarchical materials for high-power and stable energy-storage/-conversion devices.

Bio-inspired Murray materials for mass transfer and activity

NASA Astrophysics Data System (ADS)

Zheng, Xianfeng; Shen, Guofang; Wang, Chao; Li, Yu; Dunphy, Darren; Hasan, Tawfique; Brinker, C. Jeffrey; Su, Bao-Lian

2017-04-01

Both plants and animals possess analogous tissues containing hierarchical networks of pores, with pore size ratios that have evolved to maximize mass transport and rates of reactions. The underlying physical principles of this optimized hierarchical design are embodied in Murray's law. However, we are yet to realize the benefit of mimicking nature's Murray networks in synthetic materials due to the challenges in fabricating vascularized structures. Here we emulate optimum natural systems following Murray's law using a bottom-up approach. Such bio-inspired materials, whose pore sizes decrease across multiple scales and finally terminate in size-invariant units like plant stems, leaf veins and vascular and respiratory systems provide hierarchical branching and precise diameter ratios for connecting multi-scale pores from macro to micro levels. Our Murray material mimics enable highly enhanced mass exchange and transfer in liquid-solid, gas-solid and electrochemical reactions and exhibit enhanced performance in photocatalysis, gas sensing and as Li-ion battery electrodes.

Photonics and plasmonics go viral: self-assembly of hierarchical metamaterials

DOE PAGES

Wen, Amy M.; Podgornik, Rudolf; Strangi, Giuseppe; ...

2015-03-05

Sizing and shaping of mesoscale architectures with nanoscale features is a key opportunity to produce the next generation of higher-performing products and at the same time unveil completely new phenomena. This review article discusses recent advances in the design of novel photonic and plasmonic structures using a biology-inspired design. The proteinaceous capsids from viruses have long been discovered as platform technologies enabling unique applications in nanotechnology, materials, bioengineering, and medicine. In the context of materials applications, the highly organized structures formed by viral capsid proteins provide a 3D scaffold for the precise placement of plasmon and gain materials. Based onmore » their highly symmetrical structures, virus-based nanoparticles have a high propensity to self-assemble into higher-order crystalline structures, yielding hierarchical hybrid materials. Recent advances in the field have led to the development of virus-based light harvesting systems, plasmonic structures for application in high-performance metamaterials, binary nanoparticle lattices, and liquid crystalline arrays for sensing or display technologies. In conclusion, there is still much that could be explored in this area, and we foresee that this is only the beginning of great technological advances in virus-based materials for plasmonics and photonics applications.« less

Silk-regulated hierarchical hollow magnetite/carbon nanocomposite spheroids for lithium-ion battery anodes.

PubMed

Sheng, Weiqin; Zhu, Guobin; Kaplan, David L; Cao, Chuanbao; Zhu, Hesun; Lu, Qiang

2015-03-20

Hierarchical olive-like structured carbon-Fe3O4 nanocomposite particles composed of a hollow interior and a carbon coated surface are prepared by a facile, silk protein-assisted hydrothermal method. Silk nanofibers as templates and carbon precursors first regulate the formation of hollow Fe2O3 microspheres and then they are converted into carbon by a reduction process into Fe3O4. This process significantly simplifies the fabrication and carbon coating processes to form complex hollow structures. When tested as anode materials for lithium-ion batteries, these hollow carbon-coated particles exhibit high capacity (900 mAh g(-1)), excellent cycle stability (180 cycles) and rate performance due to their unique hierarchical hollow structure and carbon coating.

Construction of hierarchical porous NiCo{sub 2}O{sub 4} films composed of nanowalls as cathode materials for high-performance supercapacitor

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

Zheng, Qingyun, E-mail: hizhengqingyun@126.com; Zhang, Xiangyang; Shen, Youming

Graphical abstract: Hydrothermal-synthesized NiCo{sub 2}O{sub 4} mesowall films exhibit porous structure and high capacity as well as good cycling life for supercapacitor application. - Highlights: • Hierarchical porous NiCo{sub 2}O{sub 4} nanowall films are prepared by a hydrothermal method. • NiCo{sub 2}O{sub 4} nanowall films show excellent electrochemical performance. • Hierarchical porous film structure is favorable for fast ion/electron transfer. - Abstract: Hierarchical porous NiCo{sub 2}O{sub 4} films composed of nanowalls on nickel foam are synthesized via a facile hydrothermal method. Besides the mesoporous walls, the NiCo{sub 2}O{sub 4} nanowalls are interconnected with each other to form hierarchical porous structure.more » These unique porous structured films possess a high specific surface area. The supercapacitor performance of the hierarchical porous NiCo{sub 2}O{sub 4} film is fully characterized. A high capacity of 130 mA h g{sup −1} is achieved at 2 A g{sup −1} with 97% capacity maintained after 2,000 cycles. Importantly, 75.6% of capacity is retained when the current density changes from 3 A g{sup −1} to 36 A g{sup −1}. The superior electrochemical performance is mainly due to the unique hierarchical porous structure with large surface area as well as shorter diffusion length for ion and charge transport.« less

Electroactive nanoparticle directed assembly of functionalized graphene nanosheets into hierarchical structures with hybrid compositions for flexible supercapacitors

NASA Astrophysics Data System (ADS)

Choi, Bong Gill; Huh, Yun Suk; Hong, Won Hi; Erickson, David; Park, Ho Seok

2013-04-01

Hierarchical structures of hybrid materials with the controlled compositions have been shown to offer a breakthrough for energy storage and conversion. Here, we report the integrative assembly of chemically modified graphene (CMG) building blocks into hierarchical complex structures with the hybrid composition for high performance flexible pseudocapacitors. The formation mechanism of hierarchical CMG/Nafion/RuO2 (CMGNR) microspheres, which is triggered by the cooperative interplay during the in situ synthesis of RuO2 nanoparticles (NPs), was extensively investigated. In particular, the hierarchical CMGNR microspheres consisting of the aggregates of CMG/Nafion (CMGN) nanosheets and RuO2 NPs provided large surface area and facile ion accessibility to storage sites, while the interconnected nanosheets offered continuous electron pathways and mechanical integrity. The synergistic effect of CMGNR hybrids on the supercapacitor (SC) performance was derived from the hybrid composition of pseudocapacitive RuO2 NPs with the conductive CMGNs as well as from structural features. Consequently, the CMGNR-SCs showed a specific capacitance as high as 160 F g-1, three-fold higher than that of conventional graphene SCs, and a capacitance retention of >95% of the maximum value even after severe bending and 1000 charge-discharge tests due to the structural and compositional features.Hierarchical structures of hybrid materials with the controlled compositions have been shown to offer a breakthrough for energy storage and conversion. Here, we report the integrative assembly of chemically modified graphene (CMG) building blocks into hierarchical complex structures with the hybrid composition for high performance flexible pseudocapacitors. The formation mechanism of hierarchical CMG/Nafion/RuO2 (CMGNR) microspheres, which is triggered by the cooperative interplay during the in situ synthesis of RuO2 nanoparticles (NPs), was extensively investigated. In particular, the hierarchical CMGNR microspheres consisting of the aggregates of CMG/Nafion (CMGN) nanosheets and RuO2 NPs provided large surface area and facile ion accessibility to storage sites, while the interconnected nanosheets offered continuous electron pathways and mechanical integrity. The synergistic effect of CMGNR hybrids on the supercapacitor (SC) performance was derived from the hybrid composition of pseudocapacitive RuO2 NPs with the conductive CMGNs as well as from structural features. Consequently, the CMGNR-SCs showed a specific capacitance as high as 160 F g-1, three-fold higher than that of conventional graphene SCs, and a capacitance retention of >95% of the maximum value even after severe bending and 1000 charge-discharge tests due to the structural and compositional features. Electronic supplementary information (ESI) available: Electrodeposition procedure, TEM, SEM, and AFM images, XPS, FT-IR, and XRD spectra, mechanical strain-stress curve, textural and conductive properties, and impedance spectroscopy. See DOI: 10.1039/c3nr33674c

Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications.

PubMed

Zhang, Bin; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Song, Shuqin; Chen, Guohua; Meng, Yuezhong

2014-08-13

Novel hierarchically porous carbon materials with very high surface areas, large pore volumes and high electron conductivities were prepared from silk cocoon by carbonization with KOH activation. The prepared novel porous carbon-encapsulated sulfur composites were fabricated by a simple melting process and used as cathodes for lithium sulfur batteries. Because of the large surface area and hierarchically porous structure of the carbon material, soluble polysulfide intermediates can be trapped within the cathode and the volume expansion can be alleviated effectively. Moreover, the electron transport properties of the carbon materials can provide an electron conductive network and promote the utilization rate of sulfur in cathode. The prepared carbon-sulfur composite exhibited a high specific capacity and excellent cycle stability. The results show a high initial discharge capacity of 1443 mAh g(-1) and retain 804 mAh g(-1) after 80 discharge/charge cycles at a rate of 0.5 C. A Coulombic efficiency retained up to 92% after 80 cycles. The prepared hierarchically porous carbon materials were proven to be an effective host matrix for sulfur encapsulation to improve the sulfur utilization rate and restrain the dissolution of polysulfides into lithium-sulfur battery electrolytes.

Biomimetic Hierarchical Assembly of Helical Supraparticles from Chiral Nanoparticles

DOE PAGES

Zhou, Yunlong; Marson, Ryan L.; van Anders, Greg; ...

2016-02-22

Chiroptical materials found in butterflies, beetles, stomatopod crustaceans, and other creatures are attributed to biocomposites with helical motifs and multiscale hierarchical organization. These structurally sophisticated materials self-assemble from primitive nanoscale building blocks, a process that is simpler and more energy efficient than many top-down methods currently used to produce similarly sized three-dimensional materials. In this paper, we report that molecular-scale chirality of a CdTe nanoparticle surface can be translated to nanoscale helical assemblies, leading to chiroptical activity in the visible electromagnetic range. Chiral CdTe nanoparticles coated with cysteine self-organize around Te cores to produce helical supraparticles. D-/L-Form of the aminomore » acid determines the dominant left/right helicity of the supraparticles. Coarse-grained molecular dynamics simulations with a helical pair-potential confirm the assembly mechanism and the origin of its enantioselectivity, providing a framework for engineering three-dimensional chiral materials by self-assembly. Finally, the helical supraparticles further self-organize into lamellar crystals with liquid crystalline order, demonstrating the possibility of hierarchical organization and with multiple structural motifs and length scales determined by molecular-scale asymmetry of nanoparticle interactions.« less

Synthesis of hierarchical mesoporous lithium nickel cobalt manganese oxide spheres with high rate capability for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tong, Wei; Huang, Yudai; Cai, Yanjun; Guo, Yong; Wang, Xingchao; Jia, Dianzeng; Sun, Zhipeng; Pang, Weikong; Guo, Zaiping; Zong, Jun

2018-01-01

Hierarchical mesoporous LiNi1/3Co1/3Mn1/3O2 spheres have been synthesized by urea-assisted solvothermal method with adding Triton X-100. The structure and morphology of the as-prepared materials were analyzed by X-ray diffraction and electron microscope. The results show that the as-prepared samples can be indexed as hexagonal layered structure with hierarchical architecture, and the possible formation mechanism is speculated. When evaluated as cathode material, the hierarchical mesoporous LiNi1/3Co1/3Mn1/3O2 spheres show good electrochemical properties with high initial discharge capacity of 129.9 mAh g-1, and remain the discharge capacity of 95.5 mAh g-1 after 160 cycles at 10C. The excellent electrochemical performance of the as-prepared sample can be attributed to its stable hierarchical mesoporous framework in conjunction with large specific surface, low cation mixing and small particle size. They not only provide a large number of reaction sites for surface or interface reaction, but also shorten the diffusion length of Li+ ions. Meanwhile, the mesoporous spheres composed of nanoparticles can contribute to high rate ability and buffer volume changes during charge/discharge process.

Matriarch: A Python Library for Materials Architecture.

PubMed

Giesa, Tristan; Jagadeesan, Ravi; Spivak, David I; Buehler, Markus J

2015-10-12

Biological materials, such as proteins, often have a hierarchical structure ranging from basic building blocks at the nanoscale (e.g., amino acids) to assembled structures at the macroscale (e.g., fibers). Current software for materials engineering allows the user to specify polypeptide chains and simple secondary structures prior to molecular dynamics simulation, but is not flexible in terms of the geometric arrangement of unequilibrated structures. Given some knowledge of a larger-scale structure, instructing the software to create it can be very difficult and time-intensive. To this end, the present paper reports a mathematical language, using category theory, to describe the architecture of a material, i.e., its set of building blocks and instructions for combining them. While this framework applies to any hierarchical material, here we concentrate on proteins. We implement this mathematical language as an open-source Python library called Matriarch. It is a domain-specific language that gives the user the ability to create almost arbitrary structures with arbitrary amino acid sequences and, from them, generate Protein Data Bank (PDB) files. In this way, Matriarch is more powerful than commercial software now available. Matriarch can be used in tandem with molecular dynamics simulations and helps engineers design and modify biologically inspired materials based on their desired functionality. As a case study, we use our software to alter both building blocks and building instructions for tropocollagen, and determine their effect on its structure and mechanical properties.

Panoscopic approach for high-performance Te-doped skutterudite

DOE PAGES

Liang, Tao; Su, Xianli; Yan, Yonggao; ...

2017-02-24

One-step plasma-activated sintering (OS-PAS) fabrication of single-phase high-performance CoSb 3-based skutterudite thermoelectric material with a hierarchical structure on a time scale of a few minutes is first reported here. The formation mechanism of the CoSb 3 phase and the effects of the current and pressure fields on the phase transformation and microstructure evolution are studied in the one-step PAS process. The application of the panoscopic approach to this system and its effect on the transport properties are investigated. The results show that the hierarchical structure forms during the formation of the skutterudite phase under the effects of both current andmore » sintering pressure. The samples fabricated by the OS-PAS technique have defined hierarchical structures, which scatter phonons more intensely over a broader range of frequencies and significantly reduce the lattice thermal conductivity. High-performance bulk Te-doped skutterudite with the maximum ZT of 1.1 at 820 K for the composition CoSb 2.875Te 0.125 was obtained. Such high ZT values rival those obtained from single filled skutterudites. As a result, this newly developed OS-PAS technique enhances the thermoelectric performance, dramatically shortens the synthesis period and provides a facile method for obtaining hierarchical thermoelectric materials on a large scale.« less

Mass production of bulk artificial nacre with excellent mechanical properties.

PubMed

Gao, Huai-Ling; Chen, Si-Ming; Mao, Li-Bo; Song, Zhao-Qiang; Yao, Hong-Bin; Cölfen, Helmut; Luo, Xi-Sheng; Zhang, Fu; Pan, Zhao; Meng, Yu-Feng; Ni, Yong; Yu, Shu-Hong

2017-08-18

Various methods have been exploited to replicate nacre features into artificial structural materials with impressive structural and mechanical similarity. However, it is still very challenging to produce nacre-mimetics in three-dimensional bulk form, especially for further scale-up. Herein, we demonstrate that large-sized, three-dimensional bulk artificial nacre with comprehensive mimicry of the hierarchical structures and the toughening mechanisms of natural nacre can be facilely fabricated via a bottom-up assembly process based on laminating pre-fabricated two-dimensional nacre-mimetic films. By optimizing the hierarchical architecture from molecular level to macroscopic level, the mechanical performance of the artificial nacre is superior to that of natural nacre and many engineering materials. This bottom-up strategy has no size restriction or fundamental barrier for further scale-up, and can be easily extended to other material systems, opening an avenue for mass production of high-performance bulk nacre-mimetic structural materials in an efficient and cost-effective way for practical applications.Artificial materials that replicate the mechanical properties of nacre represent important structural materials, but are difficult to produce in bulk. Here, the authors exploit the bottom-up assembly of 2D nacre-mimetic films to fabricate 3D bulk artificial nacre with an optimized architecture and excellent mechanical properties.

Soft- to network hard-material for constructing both ion- and electron-conductive hierarchical porous structure to significantly boost energy density of a supercapacitor.

PubMed

Yang, Pingping; Xie, Jiale; Guo, Chunxian; Li, Chang Ming

2017-01-01

Soft-material PEDOT is used to network hard Co 3 O 4 nanowires for constructing both ion- and electron-conductive hierarchical porous structure Co 3 O 4 /PEDOT to greatly boost the capacitor energy density than sum of that of plain Co 3 O 4 nanowires and PEDOT film. Specifically, the networked hierarchical porous structure of Co 3 O 4 /PEDOT is synthesized and tailored through hydrothermal method and post-electrochemical polymerization method for the PEDOT coating onto Co 3 O 4 nanowires. Typically, Co 3 O 4 /PEDOT supercapacitor gets a highest areal capacitance of 160mFcm -2 at a current density of 0.2mAcm -2 , which is about 2.2 times larger than the sum of that of plain Co 3 O 4 NWs (0.92mFcm -2 ) and PEDOT film (69.88mFcm -2 ). Besides, if only PEDOT as active mass is counted, Co 3 O 4 /PEDOT cell can achieve a highest capacitance of 567.21Fg -1 , this is the highest capacitance value obtained by PEDOT-based supercapacitors. Furthermore, this soft-hard network porous structure also achieves a high cycling stability of 93% capacitance retention after the 20,000th cycle. This work demonstrates a new approach to constructing both ion and electron conductive hierarchical porous structure to significantly boost energy density of a supercapacitor. Copyright © 2016 Elsevier Inc. All rights reserved.

A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

NASA Astrophysics Data System (ADS)

Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

2016-01-01

Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06749a

Nanowire-Assembled Hierarchical ZnCo2O4 Microstructure Integrated with a Low-Power Microheater for Highly Sensitive Formaldehyde Detection.

PubMed

Long, Hu; Harley-Trochimczyk, Anna; Cheng, Siyi; Hu, Hao; Chi, Won Seok; Rao, Ameya; Carraro, Carlo; Shi, Tielin; Tang, Zirong; Maboudian, Roya

2016-11-23

Nanowire-assembled 3D hierarchical ZnCo 2 O 4 microstructure is synthesized by a facile hydrothermal route and a subsequent annealing process. In comparison to simple nanowires, the resulting dandelion-like structure yields more open spaces between nanowires, which allow for better gas diffusion and provide more active sites for gas adsorption while maintaining good electrical conductivity. The hierarchical ZnCo 2 O 4 microstructure is integrated on a low-power microheater platform without using binders or conductive additives. The hierarchical structure of the ZnCo 2 O 4 sensing material provides reliable electrical connection across the sensing electrodes. The resulting sensor exhibits an ultralow detection limit of 3 ppb toward formaldehyde with fast response and recovery as well as good selectivity to CO, H 2 , and hydrocarbons such as n-pentane, propane, and CH 4 . The sensor only consumes ∼5.7 mW for continuous operation at 300 °C with good long-term stability. The excellent sensing performance of this hierarchical structure based sensor suggests the advantages of combining such structures with microfabricated heaters for practical low-power sensing applications.

A hierarchical porous electrode using a micron-sized honeycomb-like carbon material for high capacity lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Li, Jing; Zhang, Huamin; Zhang, Yining; Wang, Meiri; Zhang, Fengxiang; Nie, Hongjiao

2013-05-01

A micron-sized honeycomb-like carbon material (MHC) is prepared in a facile way using nano-CaCO3 as a hard template. A novel electrode for lithium-oxygen batteries is fabricated and displays a superior discharge capacity as high as 5862 mA h g-1. The higher electrode space utilization is attributed to its hierarchical pore structure, with intrinsic mesopores in the MHC particles for Li2O2 depositions and macropores among them for oxygen transport.A micron-sized honeycomb-like carbon material (MHC) is prepared in a facile way using nano-CaCO3 as a hard template. A novel electrode for lithium-oxygen batteries is fabricated and displays a superior discharge capacity as high as 5862 mA h g-1. The higher electrode space utilization is attributed to its hierarchical pore structure, with intrinsic mesopores in the MHC particles for Li2O2 depositions and macropores among them for oxygen transport. Electronic supplementary information (ESI) available: Synthesis of the MHC material. Cathode preparation. Material characterization. Assembly of Li-O2 battery cells and performance evaluation. SEM image of the CaCO3-sucrose composite before carbonization. See DOI: 10.1039/c3nr00337j

Hierarchical MoS2 tubular structures internally wired by carbon nanotubes as a highly stable anode material for lithium-ion batteries

PubMed Central

Chen, Yu Ming; Yu, Xin Yao; Li, Zhen; Paik, Ungyu; Lou, Xiong Wen (David)

2016-01-01

Molybdenum disulfide (MoS2), a typical two-dimensional material, is a promising anode material for lithium-ion batteries because it has three times the theoretical capacity of graphite. The main challenges associated with MoS2 anodes are the structural degradation and the low rate capability caused by the low intrinsic electric conductivity and large strain upon cycling. Here, we design hierarchical MoS2 tubular structures internally wired by carbon nanotubes (CNTs) to tackle these problems. These porous MoS2 tubular structures are constructed from building blocks of ultrathin nanosheets, which are believed to benefit the electrochemical reactions. Benefiting from the unique structural and compositional characteristics, these CNT-wired MoS2 tubular structures deliver a very high specific capacity of ~1320 mAh g−1 at a current density of 0.1 A g−1, exceptional rate capability, and an ultralong cycle life of up to 1000 cycles. This work may inspire new ideas for constructing high-performance electrodes for electrochemical energy storage. PMID:27453938

Three-dimensional microarchitected materials and devices using nanoparticle assembly by pointwise spatial printing.

PubMed

Saleh, Mohammad Sadeq; Hu, Chunshan; Panat, Rahul

2017-03-01

Three-dimensional (3D) hierarchical materials are important to a wide range of emerging technological applications. We report a method to synthesize complex 3D microengineered materials, such as microlattices, with nearly fully dense truss elements with a minimum diameter of approximately 20 μm and having high aspect ratios (up to 20:1) without using any templating or supporting materials. By varying the postprocessing conditions, we have also introduced an additional control over the internal porosity of the truss elements to demonstrate a hierarchical porous structure with an overall void size and feature size control of over five orders of magnitudes in length scale. The method uses direct printing of nanoparticle dispersions using the Aerosol Jet technology in 3D space without templating or supporting materials followed by binder removal and sintering. In addition to 3D microlattices, we have also demonstrated directly printed stretchable interconnects, spirals, and pillars. This assembly method could be implemented by a variety of microdroplet generation methods for fast and large-scale fabrication of the hierarchical materials for applications in tissue engineering, ultralight or multifunctional materials, microfluidics, and micro-optoelectronics.

Materiomics: biological protein materials, from nano to macro.

PubMed

Cranford, Steven; Buehler, Markus J

2010-11-12

Materiomics is an emerging field of science that provides a basis for multiscale material system characterization, inspired in part by natural, for example, protein-based materials. Here we outline the scope and explain the motivation of the field of materiomics, as well as demonstrate the benefits of a materiomic approach in the understanding of biological and natural materials as well as in the design of de novo materials. We discuss recent studies that exemplify the impact of materiomics - discovering Nature's complexity through a materials science approach that merges concepts of material and structure throughout all scales and incorporates feedback loops that facilitate sensing and resulting structural changes at multiple scales. The development and application of materiomics is illustrated for the specific case of protein-based materials, which constitute the building blocks of a variety of biological systems such as tendon, bone, skin, spider silk, cells, and tissue, as well as natural composite material systems (a combination of protein-based and inorganic constituents) such as nacre and mollusk shells, and other natural multiscale systems such as cellulose-based plant and wood materials. An important trait of these materials is that they display distinctive hierarchical structures across multiple scales, where molecular details are exhibited in macroscale mechanical responses. Protein materials are intriguing examples of materials that balance multiple tasks, representing some of the most sustainable material solutions that integrate structure and function despite severe limitations in the quality and quantity of material building blocks. However, up until now, our attempts to analyze and replicate Nature's materials have been hindered by our lack of fundamental understanding of these materials' intricate hierarchical structures, scale-bridging mechanisms, and complex material components that bestow protein-based materials their unique properties. Recent advances in analytical tools and experimental methods allow a holistic view of such a hierarchical biological material system. The integration of these approaches and amalgamation of material properties at all scale levels to develop a complete description of a material system falls within the emerging field of materiomics. Materiomics is the result of the convergence of engineering and materials science with experimental and computational biology in the context of natural and synthetic materials. Through materiomics, fundamental advances in our understanding of structure-property-process relations of biological systems contribute to the mechanistic understanding of certain diseases and facilitate the development of novel biological, biologically inspired, and completely synthetic materials for applications in medicine (biomaterials), nanotechnology, and engineering.

Hierarchical mesostructured titanium phosphonates with unusual uniform lines of macropores.

PubMed

Ma, Tian-Yi; Lin, Xiu-Zhen; Zhang, Xue-Jun; Yuan, Zhong-Yong

2011-04-01

Organic-inorganic hybrid materials of mesostructured titanium phosphonates with unusual uniform lines of macropores were synthesized by using bis(hexamethylenetriamine) penta(methylenephosphonic acid) (BHMTPMP) as the coupling molecule, through a one-pot hydrothermal process without any surfactant assistance. A wormhole-like mesostructure and many uniform parallel lines of macropores divided by solid ridges in the same direction were confirmed by N(2) sorption, SEM and TEM observations. This novel macropore architecture has never been observed in other metal phosphonate materials, which may be directly related to the structure nature of BHMTPMP with extra long alkyl chains. The structural characterization of FT-IR and MAS NMR revealed the integrity of organic groups inside the hybrid framework. The hybrid materials were also used as adsorbents for heavy metal ions and CO(2), in order to clarify the impacts of the organic contents and organic types on the physicochemical properties of the synthesized hierarchical macro-/mesoporous phosphonate materials.

Artificial 3D hierarchical and isotropic porous polymeric materials

PubMed Central

Musteata, Valentina-Elena; Behzad, Ali Reza

2018-01-01

Hierarchical porous materials that replicate complex living structures are attractive for a wide variety of applications, ranging from storage and catalysis to biological and artificial systems. However, the preparation of structures with a high level of complexity and long-range order at the mesoscale and microscale is challenging. We report a simple, nonextractive, and nonreactive method used to prepare three-dimensional porous materials that mimic biological systems such as marine skeletons and honeycombs. This method exploits the concurrent occurrence of the self-assembly of block copolymers in solution and macrophase separation by nucleation and growth. We obtained a long-range order of micrometer-sized compartments. These compartments are interconnected by ordered cylindrical nanochannels. The new approach is demonstrated using polystyrene-b-poly(t-butyl acrylate), which can be further explored for a broad range of applications, such as air purification filters for viruses and pollution particle removal or growth of bioinspired materials for bone regeneration.

Artificial 3D hierarchical and isotropic porous polymeric materials.

PubMed

Chisca, Stefan; Musteata, Valentina-Elena; Sougrat, Rachid; Behzad, Ali Reza; Nunes, Suzana P

2018-05-01

Hierarchical porous materials that replicate complex living structures are attractive for a wide variety of applications, ranging from storage and catalysis to biological and artificial systems. However, the preparation of structures with a high level of complexity and long-range order at the mesoscale and microscale is challenging. We report a simple, nonextractive, and nonreactive method used to prepare three-dimensional porous materials that mimic biological systems such as marine skeletons and honeycombs. This method exploits the concurrent occurrence of the self-assembly of block copolymers in solution and macrophase separation by nucleation and growth. We obtained a long-range order of micrometer-sized compartments. These compartments are interconnected by ordered cylindrical nanochannels. The new approach is demonstrated using polystyrene- b -poly( t -butyl acrylate), which can be further explored for a broad range of applications, such as air purification filters for viruses and pollution particle removal or growth of bioinspired materials for bone regeneration.

Emergence of the interplay between hierarchy and contact splitting in biological adhesion highlighted through a hierarchical shear lag model.

PubMed

Brely, Lucas; Bosia, Federico; Pugno, Nicola M

2018-06-20

Contact unit size reduction is a widely studied mechanism as a means to improve adhesion in natural fibrillar systems, such as those observed in beetles or geckos. However, these animals also display complex structural features in the way the contact is subdivided in a hierarchical manner. Here, we study the influence of hierarchical fibrillar architectures on the load distribution over the contact elements of the adhesive system, and the corresponding delamination behaviour. We present an analytical model to derive the load distribution in a fibrillar system loaded in shear, including hierarchical splitting of contacts, i.e. a "hierarchical shear-lag" model that generalizes the well-known shear-lag model used in mechanics. The influence on the detachment process is investigated introducing a numerical procedure that allows the derivation of the maximum delamination force as a function of the considered geometry, including statistical variability of local adhesive energy. Our study suggests that contact splitting generates improved adhesion only in the ideal case of extremely compliant contacts. In real cases, to produce efficient adhesive performance, contact splitting needs to be coupled with hierarchical architectures to counterbalance high load concentrations resulting from contact unit size reduction, generating multiple delamination fronts and helping to avoid detrimental non-uniform load distributions. We show that these results can be summarized in a generalized adhesion scaling scheme for hierarchical structures, proving the beneficial effect of multiple hierarchical levels. The model can thus be used to predict the adhesive performance of hierarchical adhesive structures, as well as the mechanical behaviour of composite materials with hierarchical reinforcements.

Electroactive nanoparticle directed assembly of functionalized graphene nanosheets into hierarchical structures with hybrid compositions for flexible supercapacitors.

PubMed

Choi, Bong Gill; Huh, Yun Suk; Hong, Won Hi; Erickson, David; Park, Ho Seok

2013-05-07

Hierarchical structures of hybrid materials with the controlled compositions have been shown to offer a breakthrough for energy storage and conversion. Here, we report the integrative assembly of chemically modified graphene (CMG) building blocks into hierarchical complex structures with the hybrid composition for high performance flexible pseudocapacitors. The formation mechanism of hierarchical CMG/Nafion/RuO2 (CMGNR) microspheres, which is triggered by the cooperative interplay during the in situ synthesis of RuO2 nanoparticles (NPs), was extensively investigated. In particular, the hierarchical CMGNR microspheres consisting of the aggregates of CMG/Nafion (CMGN) nanosheets and RuO2 NPs provided large surface area and facile ion accessibility to storage sites, while the interconnected nanosheets offered continuous electron pathways and mechanical integrity. The synergistic effect of CMGNR hybrids on the supercapacitor (SC) performance was derived from the hybrid composition of pseudocapacitive RuO2 NPs with the conductive CMGNs as well as from structural features. Consequently, the CMGNR-SCs showed a specific capacitance as high as 160 F g(-1), three-fold higher than that of conventional graphene SCs, and a capacitance retention of >95% of the maximum value even after severe bending and 1000 charge-discharge tests due to the structural and compositional features.

Fabrication of hierarchically branched SnO2 nanowires by two-step deposition method and their applications to electrocatalyst support and Li ion electrode

NASA Astrophysics Data System (ADS)

Lee, Sang Ho; Jo, Yong-Ryun; Noh, Yuseong; Kim, Bong-Joong; Kim, Won Bae

2017-11-01

This paper reports hierarchically branched structures of tin dioxide nanowires for use in electrochemical energy conversion and storage electrode systems. The shallow tin dioxide branches are epitaxially grown on the tin dioxide nanowire backbones that are directly formed on current collectors. The branched tin dioxide nanowires are applied as anode electrodes for lithium-ion batteries, while palladium-incorporated branched nanowires are utilized as electrocatalysts for ethanol electrooxidation reactions. The structural benefits of these hierarchical platforms, such as enlarged electrochemical active surface area, void space formed between the branched structures, and conformal contact of the electroactive materials with current collectors, play important roles in improving the electrochemical Li-ion storage as well as electrocatalytic activity.

Synergistic effects from graphene and carbon nanotubes endow ordered hierarchical structure foams with a combination of compressibility, super-elasticity and stability and potential application as pressure sensors.

PubMed

Kuang, Jun; Dai, Zhaohe; Liu, Luqi; Yang, Zhou; Jin, Ming; Zhang, Zhong

2015-01-01

Nanostructured carbon material based three-dimensional porous architectures have been increasingly developed for various applications, e.g. sensors, elastomer conductors, and energy storage devices. Maintaining architectures with good mechanical performance, including elasticity, load-bearing capacity, fatigue resistance and mechanical stability, is prerequisite for realizing these functions. Though graphene and CNT offer opportunities as nanoscale building blocks, it still remains a great challenge to achieve good mechanical performance in their microarchitectures because of the need to precisely control the structure at different scales. Herein, we fabricate a hierarchical honeycomb-like structured hybrid foam based on both graphene and CNT. The resulting materials possess excellent properties of combined high specific strength, elasticity and mechanical stability, which cannot be achieved in neat CNT and graphene foams. The improved mechanical properties are attributed to the synergistic-effect-induced highly organized, multi-scaled hierarchical architectures. Moreover, with their excellent electrical conductivity, we demonstrated that the hybrid foams could be used as pressure sensors in the fields related to artificial skin.

Microfluidic Droplet-Facilitated Hierarchical Assembly for Dual Cargo Loading and Synergistic Delivery.

PubMed

Yu, Ziyi; Zheng, Yu; Parker, Richard M; Lan, Yang; Wu, Yuchao; Coulston, Roger J; Zhang, Jing; Scherman, Oren A; Abell, Chris

2016-04-06

Bottom-up hierarchical assembly has emerged as an elaborate and energy-efficient strategy for the fabrication of smart materials. Herein, we present a hierarchical assembly process, whereby linear amphiphilic block copolymers are self-assembled into micelles, which in turn are accommodated at the interface of microfluidic droplets via cucurbit[8]uril-mediated host-guest chemistry to form supramolecular microcapsules. The monodisperse microcapsules can be used for simultaneous carriage of both organic (Nile Red) and aqueous-soluble (fluorescein isothiocyanate-dextran) cargo. Furthermore, the well-defined compartmentalized structure benefits from the dynamic nature of the supramolecular interaction and offers synergistic delivery of cargos with triggered release or through photocontrolled porosity. This demonstration of premeditated hierarchical assembly, where interactions from the molecular to microscale are designed, illustrates the power of this route toward accessing the next generation of functional materials and encapsulation strategies.

Hierarchical meso/macro-porous carbon fabricated from dual MgO templates for direct electron transfer enzymatic electrodes.

PubMed

Funabashi, Hiroto; Takeuchi, Satoshi; Tsujimura, Seiya

2017-03-23

We designed a three-dimensional (3D) hierarchical pore structure to improve the current production efficiency and stability of direct electron transfer-type biocathodes. The 3D hierarchical electrode structure was fabricated using a MgO-templated porous carbon framework produced from two MgO templates with sizes of 40 and 150 nm. The results revealed that the optimal pore composition for a bilirubin oxidase-catalysed oxygen reduction cathode was a mixture of 33% macropores and 67% mesopores (MgOC 33 ). The macropores improve mass transfer inside the carbon material, and the mesopores improve the electron transfer efficiency of the enzyme by surrounding the enzyme with carbon.

Hierarchical meso/macro-porous carbon fabricated from dual MgO templates for direct electron transfer enzymatic electrodes

NASA Astrophysics Data System (ADS)

Funabashi, Hiroto; Takeuchi, Satoshi; Tsujimura, Seiya

2017-03-01

We designed a three-dimensional (3D) hierarchical pore structure to improve the current production efficiency and stability of direct electron transfer-type biocathodes. The 3D hierarchical electrode structure was fabricated using a MgO-templated porous carbon framework produced from two MgO templates with sizes of 40 and 150 nm. The results revealed that the optimal pore composition for a bilirubin oxidase-catalysed oxygen reduction cathode was a mixture of 33% macropores and 67% mesopores (MgOC33). The macropores improve mass transfer inside the carbon material, and the mesopores improve the electron transfer efficiency of the enzyme by surrounding the enzyme with carbon.

Construction of Hierarchical α-MnO2 Nanowires@Ultrathin δ-MnO2 Nanosheets Core-Shell Nanostructure with Excellent Cycling Stability for High-Power Asymmetric Supercapacitor Electrodes.

PubMed

Ma, Zhipeng; Shao, Guangjie; Fan, Yuqian; Wang, Guiling; Song, Jianjun; Shen, Dejiu

2016-04-13

Poor electrical conductivity and mechanical instability are two major obstacles to realizing high performance of MnO2 as pseudocapacitor material. The construction of unique hierarchical core-shell nanostructures, therefore, plays an important role in the efficient enhancement of the rate capacity and the stability of this material. We herein report the fabrication of a hierarchical α-MnO2 nanowires@ultrathin δ-MnO2 nanosheets core-shell nanostructure by adopting a facile and practical solution-phase technique. The novel hierarchical nanostructures are composed of ultrathin δ-MnO2 nanosheets with a few atomic layers growing well on the surface of the ultralong α-MnO2 nanowires. The first specific capacitance of hierarchical core-shell nanostructure reached 153.8 F g(-1) at the discharge current density of as high as 20 A g(-1), and the cycling stability is retained at 98.1% after 10,000 charge-discharge cycles, higher than those in the literature. The excellent rate capacity and stability of the hierarchical core-shell nanostructures can be attributed to the structural features of the two MnO2 crystals, in which a 1D α-MnO2 nanowire core provides a stable structural backbone and the ultrathin 2D δ-MnO2 nanosheet shell creates more reactive active sites. The synergistic effects of different dimensions also contribute to the superior rate capability.

Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis

DOE PAGES

Yue, Yanfeng; Fulvio, Pasquale F.; Dai, Sheng

2015-12-04

Metal–organic frameworks (MOFs) represent a new family of microporous materials; however, microporous–mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchicalmore » materials with larger mesopores, the latter requires a template removal step, which may result in the collapse of the implemented mesopores. Recently, a general template-free synthesis of hierarchical microporous crystalline frameworks, such as MOFs and Prussian blue analogues (PBAs), has been reported. Our new method is based on the kinetically controlled precipitation (perturbation), with simultaneous condensation and redissolution of polymorphic nanocrystallites in the mother liquor. This method further eliminates the use of extended organic ligands and the micropores do not collapse upon removal of trapped guest solvent molecules, thus yielding hierarchical MOF materials with intriguing porosity in the gram scale. The hierarchical MOF materials prepared in this way exhibited exceptional properties when tested for the adsorption of large organic dyes over their corresponding microporous frameworks, due to the enhanced pore accessibility and electrolyte diffusion within the mesopores. As for PBAs, the pore size distribution of these materials can be tailored by changing the metals substituting Fe cations in the PB lattice. For these, the textural mesopores increased from approximately 10 nm for Cu analogue (mesoCuHCF), to 16 nm in Co substituted compound (mesoCoHCF), and to as large as 30 nm for the Ni derivative (mesoNiHCF). And while bulk PB and analogues have a higher capacitance than hierarchical analogues for Na-batteries, the increased accessibility to the microporous channels of PBAs allow for faster intercalated ion exchange and diffusion than in bulk PBA crystals. Therefore, hierarchical PBAs are promising candidates for electrodes in future electrochemical energy storage devices with faster charge–discharge rates than batteries, namely pseudocapacitors. Finally, this new synthetic method opens the possibility to prepare hierarchical materials having bimodal distribution of mesopores, and to tailor the structural properties of MOFs for different applications, including contrasting agents for MRI, and drug delivery.« less

Template-free fabrication of hierarchically flower-like tungsten trioxide assemblies with enhanced visible-light-driven photocatalytic activity.

PubMed

Yu, Jiaguo; Qi, Lifang

2009-09-30

Hierarchically flower-like tungsten trioxide assemblies were fabricated on a large scale by a simple hydrothermal treatment of sodium tungstate in aqueous solution of nitric acid. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy and N(2) adsorption-desorption measurements. The photocatalytic activity was evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. It was found that the three-dimensional tungsten trioxide assemblies were constructed from two-dimensional layers, which were further composed of a large number of interconnected lathy nanoplates with different sizes. Such flower-like assemblies exhibited hierarchically porous structure and higher visible-light photocatalytic activity than the samples without such hierarchical structures due to their specific hierarchical pores that served as the transport paths for light and reactants. After five recycles for the photodegradation of RhB, the catalyst did not exhibit any great loss in activity, confirming hierarchically flower-like tungsten trioxide was stability and not photocorroded. This study may provide new insight into environmentally benign preparation and design of novel photocatalytic materials and enhancement of photocatalytic activity.

Hierarchical Tubular Structures Composed of Co3 O4 Hollow Nanoparticles and Carbon Nanotubes for Lithium Storage.

PubMed

Chen, Yu Ming; Yu, Le; Lou, Xiong Wen David

2016-05-10

Hierarchical tubular structures composed of Co3 O4 hollow nanoparticles and carbon nanotubes (CNTs) have been synthesized by an efficient multi-step route. Starting from polymer-cobalt acetate (Co(Ac)2 ) composite nanofibers, uniform polymer-Co(Ac)2 @zeolitic imidazolate framework-67 (ZIF-67) core-shell nanofibers are first synthesized via partial phase transformation with 2-methylimidazole in ethanol. After the selective dissolution of polymer-Co(Ac)2 cores, the resulting ZIF-67 tubular structures can be converted into hierarchical CNTs/Co-carbon hybrids by annealing in Ar/H2 atmosphere. Finally, the hierarchical CNT/Co3 O4 microtubes are obtained by a subsequent thermal treatment in air. Impressively, the as-prepared nanocomposite delivers a high reversible capacity of 1281 mAh g(-1) at 0.1 A g(-1) with exceptional rate capability and long cycle life over 200 cycles as an anode material for lithium-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical CaCO3 chromatography: a stationary phase based on biominerals.

PubMed

Sato, Kosuke; Oaki, Yuya; Takahashi, Daisuke; Toshima, Kazunobu; Imai, Hiroaki

2015-03-23

In biomineralization, acidic macromolecules play important roles for the growth control of crystals through a specific interaction. Inspired by this interaction, we report on an application of the hierarchical structures in CaCO3 biominerals to a stationary phase of chromatography. The separation and purification of acidic small organic molecules are achieved by thin-layer chromatography and flash chromatography using the powder of biominerals as the stationary phase. The unit nanocrystals and their oriented assembly, the hierarchical structure, are suitable for the adsorption site of the target organic molecules and the flow path of the elution solvents, respectively. The separation mode is ascribed to the specific adsorption of the acidic molecules on the crystal face and the coordination of the functional groups to the calcium ions. The results imply that a new family of stationary phase of chromatography can be developed by the fine tuning of hierarchical structures in CaCO3 materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantifying the Hierarchical Order in Self-Aligned Carbon Nanotubes from Atomic to Micrometer Scale.

PubMed

Meshot, Eric R; Zwissler, Darwin W; Bui, Ngoc; Kuykendall, Tevye R; Wang, Cheng; Hexemer, Alexander; Wu, Kuang Jen J; Fornasiero, Francesco

2017-06-27

Fundamental understanding of structure-property relationships in hierarchically organized nanostructures is crucial for the development of new functionality, yet quantifying structure across multiple length scales is challenging. In this work, we used nondestructive X-ray scattering to quantitatively map the multiscale structure of hierarchically self-organized carbon nanotube (CNT) "forests" across 4 orders of magnitude in length scale, from 2.0 Å to 1.5 μm. Fully resolved structural features include the graphitic honeycomb lattice and interlayer walls (atomic), CNT diameter (nano), as well as the greater CNT ensemble (meso) and large corrugations (micro). Correlating orientational order across hierarchical levels revealed a cascading decrease as we probed finer structural feature sizes with enhanced sensitivity to small-scale disorder. Furthermore, we established qualitative relationships for single-, few-, and multiwall CNT forest characteristics, showing that multiscale orientational order is directly correlated with number density spanning 10 9 -10 12 cm -2 , yet order is inversely proportional to CNT diameter, number of walls, and atomic defects. Lastly, we captured and quantified ultralow-q meridional scattering features and built a phenomenological model of the large-scale CNT forest morphology, which predicted and confirmed that these features arise due to microscale corrugations along the vertical forest direction. Providing detailed structural information at multiple length scales is important for design and synthesis of CNT materials as well as other hierarchically organized nanostructures.

Fabrication of free-standing hierarchical carbon nanofiber/graphene oxide/polyaniline films for supercapacitors.

PubMed

Xu, Dongdong; Xu, Qun; Wang, Kaixi; Chen, Jun; Chen, Zhimin

2014-01-08

A hierarchical high-performance electrode with nanoacanthine-style polyaniline (PANI) deposited onto a carbon nanofiber/graphene oxide (CNF/GO) template was successfully prepared via an in situ polymerization process. The morphology analysis shows that introducing one-dimensional (1D) CNF could significantly decrease/inhibit the staking of laminated GO to form an open-porous CNF/GO architecture. Followed with in situ facial deposition of PANI, the as-synthesized PANI modified CNF/GO exhibits three-dimensional (3D) hierarchical layered nanoarchitecture, which favors the diffusion of the electrolyte ions into the inner region of active materials. The hierarchical free-standing electrodes were directly fabricated into sandwich structured supercapacitors using 1 M H2SO4 as the electrolyte showing a significant specific capacitance of 450.2 F/g at the voltage scan rate of 10 mV/s. The electrochemical properties of the hierarchical structure can be further improved by a reduction procedure of GO before the deposition of PANI.

Understanding Diffusion in Hierarchical Zeolites with House-of-Cards Nanosheets.

PubMed

Bai, Peng; Haldoupis, Emmanuel; Dauenhauer, Paul J; Tsapatsis, Michael; Siepmann, J Ilja

2016-08-23

Introducing mesoporosity to conventional microporous sorbents or catalysts is often proposed as a solution to enhance their mass transport rates. Here, we show that diffusion in these hierarchical materials is more complex and exhibits non-monotonic dependence on sorbate loading. Our atomistic simulations of n-hexane in a model system containing microporous nanosheets and mesopore channels indicate that diffusivity can be smaller than in a conventional zeolite with the same micropore structure, and this observation holds true even if we confine the analysis to molecules completely inside the microporous nanosheets. Only at high sorbate loadings or elevated temperatures, when the mesopores begin to be sufficiently populated, does the overall diffusion in the hierarchical material exceed that in conventional microporous zeolites. Our model system is free of structural defects, such as pore blocking or surface disorder, that are typically invoked to explain slower-than-expected diffusion phenomena in experimental measurements. Examination of free energy profiles and visualization of molecular diffusion pathways demonstrates that the large free energy cost (mostly enthalpic in origin) for escaping from the microporous region into the mesopores leads to more tortuous diffusion paths and causes this unusual transport behavior in hierarchical nanoporous materials. This knowledge allows us to re-examine zero-length-column chromatography data and show that these experimental measurements are consistent with the simulation data when the crystallite size instead of the nanosheet thickness is used for the nominal diffusional length.

Formation of Hierarchical Cu-Doped CoSe2 Microboxes via Sequential Ion Exchange for High-Performance Sodium-Ion Batteries.

PubMed

Fang, Yongjin; Yu, Xin-Yao; Lou, Xiong Wen David

2018-04-06

Electrode materials based on electrochemical conversion reactions have received considerable interest for high capacity anodes of sodium-ion batteries. However, their practical application is greatly hindered by the poor rate capability and rapid capacity fading. Tuning the structure at nanoscale and increasing the conductivity of these anode materials are two effective strategies to address these issues. Herein, a two-step ion-exchange method is developed to synthesize hierarchical Cu-doped CoSe 2 microboxes assembled by ultrathin nanosheets using Co-Co Prussian blue analogue microcubes as the starting material. Benefitting from the structural and compositional advantages, these Cu-doped CoSe 2 microboxes with improved conductivity exhibit enhanced sodium storage properties in terms of good rate capability and excellent cycling performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon coated SnO2 nanoparticles anchored on CNT as a superior anode material for lithium-ion batteries.

PubMed

Ma, Chunrong; Zhang, Weimin; He, Yu-Shi; Gong, Qiang; Che, Haiying; Ma, Zi-Feng

2016-02-21

Hierarchically structured carbon coated SnO2 nanoparticles well-anchored on the surface of a CNT (C-SnO2/CNT) material were synthesized by a facile hydrothermal process and subsequent carbonization. The as-obtained C-SnO2/CNT hybrid, when applied as an anode material for lithium ion batteries (LIBs), showed a high reversible capacity up to 1572 mA h g(-1) at 200 mA g(-1) with a superior rate capability (685 mA h g(-1) at 4000 mA g(-1)). Even after 100 charge/discharge cycles at 1000 mA g(-1), a specific capacity of 1100 mA h g(-1) can still be maintained. Such impressive electrochemical performance can be mainly attributed to the hierarchical sandwiched structure and strong synergistic effects of the ultrafine SnO2 nanoparticles and the carbon coating, and thus presents this material a promising anode material for LIBs.

Nitrogen-doped 3D flower-like carbon materials derived from polyimide as high-performance anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wu, Qiong; Liu, Jiaqi; Yuan, Chenpei; Li, Qiang; Wang, Heng-guo

2017-12-01

Nitrogen-doped 3D flower-like carbon materials (NFCs) have been fabricated using a simple and effective strategy, namely, the hierarchical assembly of polyimide (PI) and subsequent thermal treatment. The effect of pyrolysis temperature on the structural evolution process of PI is also investigated systematically. When evaluated as anode materials for lithium ion batteries (LIBs), the as-obtained NFCs, especially NFCs-550, exhibit good electrochemical performance, including a high reversible capacity (1488.1 mAh g-1 at 0.05 A g-1), excellent rate performance (287.6 mAh g-1 at 2 A g-1), and good cycling stability (645 mAh g-1 with 96% retention after 300 cycles at 0.1 A g-1). The good electrochemical performance is attributed to the synergistic effect between 3D flower-like nanostructure and high nitrogen content. This approach may provide some inspiration to construct a series of heteroatom doped and hierarchical structured carbon materials using polymers for LIBs.

Hierarchically Porous Carbon Materials for CO 2 Capture: The Role of Pore Structure

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

Estevez, Luis; Barpaga, Dushyant; Zheng, Jian

2018-01-17

With advances in porous carbon synthesis techniques, hierarchically porous carbon (HPC) materials are being utilized as relatively new porous carbon sorbents for CO2 capture applications. These HPC materials were used as a platform to prepare samples with differing textural properties and morphologies to elucidate structure-property relationships. It was found that high microporous content, rather than overall surface area was of primary importance for predicting good CO2 capture performance. Two HPC materials were analyzed, each with near identical high surface area (~2700 m2/g) and colossally high pore volume (~10 cm3/g), but with different microporous content and pore size distributions, which ledmore » to dramatically different CO2 capture performance. Overall, large pore volumes obtained from distinct mesopores were found to significantly impact adsorption performance. From these results, an optimized HPC material was synthesized that achieved a high CO2 capacity of ~3.7 mmol/g at 25°C and 1 bar.« less

MOF-5 decorated hierarchical ZnO nanorod arrays and its photoluminescence

NASA Astrophysics Data System (ADS)

Zhang, Yinmin; Lan, Ding; Wang, Yuren; Cao, He; Jiang, Heng

2011-04-01

The strategy to manipulate nanoscale materials into well-organized hierarchical architectures is very important to both material synthesis and nanodevice applications. Here, nanoscale MOF-5 crystallites were successfully fabricated onto ordered hierarchical ZnO arrays based on aqueous chemical synthesis and molecule self-assembly technology guided room temperature diffusion method, which has the advantages of energy saving and simple operation. The structures and morphologies of the samples were performed by X-ray powder diffraction and field emission scanning electronic microscopy. The MOF-5 crystallites have good quality and bind well to the hexagonal-patterned ZnO arrays. The photoluminescence spectrum shows that the emission of hybrid MOF-5-ZnO films displays a blue shift in green emission and intensity reduction in UV emission. This ordered hybrid semiconductor material is expected to exploit the great potentiality in sensors, micro/nanodevices, and screen displays.

Mesopore quality determines the lifetime of hierarchically structured zeolite catalysts

NASA Astrophysics Data System (ADS)

Milina, Maria; Mitchell, Sharon; Crivelli, Paolo; Cooke, David; Pérez-Ramírez, Javier

2014-05-01

Deactivation due to coking limits the lifetime of zeolite catalysts in the production of chemicals and fuels. Superior performance can be achieved through hierarchically structuring the zeolite porosity, yet no relation has been established between the mesopore architecture and the catalyst lifetime. Here we introduce a top-down demetallation strategy to locate mesopores in different regions of MFI-type crystals with identical bulk porous and acidic properties. In contrast, well-established bottom-up strategies as carbon templating and seed silanization fail to yield materials with matching characteristics. Advanced characterization tools capable of accurately discriminating the mesopore size, distribution and connectivity are applied to corroborate the concept of mesopore quality. Positron annihilation lifetime spectroscopy proves powerful to quantify the global connectivity of the intracrystalline pore network, which, as demonstrated in the conversions of methanol or of propanal to hydrocarbons, is closely linked to the lifetime of zeolite catalysts. The findings emphasize the need to aptly tailor hierarchical materials for maximal catalytic advantage.

Chitin/clay microspheres with hierarchical architecture for highly efficient removal of organic dyes.

PubMed

Xu, Rui; Mao, Jie; Peng, Na; Luo, Xiaogang; Chang, Chunyu

2018-05-15

Numerous adsorbents have been reported for efficient removal of dye from water, but the high cost raw materials and complicated fabrication process limit their practical applications. Herein, novel nanocomposite microspheres were fabricated from chitin and clay by a simple thermally induced sol-gel transition. Clay nanosheets were uniformly embedded in a nanofiber weaved chitin microsphere matrix, leading to their hierarchical architecture. Benefiting from this unique structure, microspheres could efficiently remove methylene blue (MB) through a spontaneous physic-sorption process which fit well with pseudo-second-order and Langmuir isotherm models. The maximal values of adsorption capability obtained by calculation and experiment were 152.2 and 156.7 mg g -1 , respectively. Chitin/clay microspheres (CCM2) could remove 99.99% MB from its aqueous solution (10 mg g -1 ) within 20 min. These findings provide insight into a new strategy for fabrication of dye adsorbents with hierarchical structure from low cost raw materials. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hierarchical TiO2-B composed of nanosheets with exposed {010} facets as a high-performance anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Yubin; Chen, Wenqiang; Yang, Chengyu; Wei, Qiaohua; Wei, Mingdeng

2018-07-01

Facet engineering of electrode materials with a special facet provides a new strategy to enhance their electrochemical properties. In the present work, hierarchical TiO2-B composed of nanosheets with exposed {010} facets are successfully synthesized via a facial hydrothermal route. When used as an anode for lithium ion batteries, this material demonstrates high capacities, excellent rata capability and remarkable cycling performance. For instance, it displays a reversible capacity of 200.9 mA h g-1 after 200 cycles at a current density of 1.675 A g-1 (5 C). Furthermore, a full cell consisted of hierarchical TiO2-B composed of nanosheets with exposed {010} facets anode and LiFePO4 cathode exhibits a high capacity of 125.6 mA h g-1 after 1000 cycles at a current density of 2 A g-1. Such outstanding electrochemical properties of this material can be attributed to hierarchical structure and the presence of exposed {010} facets which provides favorable lithium transport channels.

Bio-inspired Murray materials for mass transfer and activity

PubMed Central

Zheng, Xianfeng; Shen, Guofang; Wang, Chao; Li, Yu; Dunphy, Darren; Hasan, Tawfique; Brinker, C. Jeffrey; Su, Bao-Lian

2017-01-01

Both plants and animals possess analogous tissues containing hierarchical networks of pores, with pore size ratios that have evolved to maximize mass transport and rates of reactions. The underlying physical principles of this optimized hierarchical design are embodied in Murray's law. However, we are yet to realize the benefit of mimicking nature's Murray networks in synthetic materials due to the challenges in fabricating vascularized structures. Here we emulate optimum natural systems following Murray's law using a bottom-up approach. Such bio-inspired materials, whose pore sizes decrease across multiple scales and finally terminate in size-invariant units like plant stems, leaf veins and vascular and respiratory systems provide hierarchical branching and precise diameter ratios for connecting multi-scale pores from macro to micro levels. Our Murray material mimics enable highly enhanced mass exchange and transfer in liquid–solid, gas–solid and electrochemical reactions and exhibit enhanced performance in photocatalysis, gas sensing and as Li-ion battery electrodes. PMID:28382972

MnO2 Nanowire/Biomass-Derived Carbon from Hemp Stem for High-Performance Supercapacitors.

PubMed

Yang, MinHo; Kim, Dong Seok; Hong, Seok Bok; Sim, Jae-Wook; Kim, Jinsoo; Kim, Seung-Soo; Choi, Bong Gill

2017-05-30

Hierarchical 3D nanostructures based on waste biomass are being offered as promising materials for energy storage due to their processabilities, multifunctionalities, environmental benignities, and low cost. Here we report a facile, inexpensive, and scalable strategy for the fabrication of hierarchical porous 3D structure as electrode materials for supercapacitors based on MnO 2 nanowires and hemp-derived activated carbon (HC). Vertical MnO 2 wires are uniformly deposited onto the surface of HC using a one-step hydrothermal method to produce hierarchical porous structures with conductive interconnected 3D networks. HC acts as a near-ideal 3D current collector and anchors electroactive materials, and this confers a specific capacitance of 340 F g -1 at 1 A g -1 with a high rate capability (88% retention) of the 3D MnO 2 /HC composite because of its open-pore system, which facilitates ion and electron transports and synergistic contribution of two energy-storage materials. Moreover, asymmetric supercapacitors fabricated using 3D HC as the anode and 3D MnO 2 /HC as the cathode are able to store 33.3 Wh kg -1 of energy and have a power delivery of 14.8 kW kg -1 .

Protein- mediated enamel mineralization

PubMed Central

Moradian-Oldak, Janet

2012-01-01

Enamel is a hard nanocomposite bioceramic with significant resilience that protects the mammalian tooth from external physical and chemical damages. The remarkable mechanical properties of enamel are associated with its hierarchical structural organization and its thorough connection with underlying dentin. This dynamic mineralizing system offers scientists a wealth of information that allows the study of basic principals of organic matrix-mediated biomineralization and can potentially be utilized in the fields of material science and engineering for development and design of biomimetic materials. This chapter will provide a brief overview of enamel hierarchical structure and properties as well as the process and stages of amelogenesis. Particular emphasis is given to current knowledge of extracellular matrix protein and proteinases, and the structural chemistry of the matrix components and their putative functions. The chapter will conclude by discussing the potential of enamel for regrowth. PMID:22652761

Structural biological composites: An overview

NASA Astrophysics Data System (ADS)

Meyers, Marc A.; Lin, Albert Y. M.; Seki, Yasuaki; Chen, Po-Yu; Kad, Bimal K.; Bodde, Sara

2006-07-01

Biological materials are complex composites that are hierarchically structured and multifunctional. Their mechanical properties are often outstanding, considering the weak constituents from which they are assembled. They are for the most part composed of brittle (often, mineral) and ductile (organic) components. These complex structures, which have risen from millions of years of evolution, are inspiring materials scientists in the design of novel materials. This paper discusses the overall design principles in biological structural composites and illustrates them for five examples; sea spicules, the abalone shell, the conch shell, the toucan and hornbill beaks, and the sheep crab exoskeleton.

A low-cost hierarchical nanostructured beta-titanium alloy with high strength

PubMed Central

Devaraj, Arun; Joshi, Vineet V.; Srivastava, Ankit; Manandhar, Sandeep; Moxson, Vladimir; Duz, Volodymyr A.; Lavender, Curt

2016-01-01

Lightweighting of automobiles by use of novel low-cost, high strength-to-weight ratio structural materials can reduce the consumption of fossil fuels and in turn CO2 emission. Working towards this goal we achieved high strength in a low cost β-titanium alloy, Ti–1Al–8V–5Fe (Ti185), by hierarchical nanostructure consisting of homogenous distribution of micron-scale and nanoscale α-phase precipitates within the β-phase matrix. The sequence of phase transformation leading to this hierarchical nanostructure is explored using electron microscopy and atom probe tomography. Our results suggest that the high number density of nanoscale α-phase precipitates in the β-phase matrix is due to ω assisted nucleation of α resulting in high tensile strength, greater than any current commercial titanium alloy. Thus hierarchical nanostructured Ti185 serves as an excellent candidate for replacing costlier titanium alloys and other structural alloys for cost-effective lightweighting applications. PMID:27034109

Materiomics: biological protein materials, from nano to macro

PubMed Central

Cranford, Steven; Buehler, Markus J

2010-01-01

Materiomics is an emerging field of science that provides a basis for multiscale material system characterization, inspired in part by natural, for example, protein-based materials. Here we outline the scope and explain the motivation of the field of materiomics, as well as demonstrate the benefits of a materiomic approach in the understanding of biological and natural materials as well as in the design of de novo materials. We discuss recent studies that exemplify the impact of materiomics – discovering Nature’s complexity through a materials science approach that merges concepts of material and structure throughout all scales and incorporates feedback loops that facilitate sensing and resulting structural changes at multiple scales. The development and application of materiomics is illustrated for the specific case of protein-based materials, which constitute the building blocks of a variety of biological systems such as tendon, bone, skin, spider silk, cells, and tissue, as well as natural composite material systems (a combination of protein-based and inorganic constituents) such as nacre and mollusk shells, and other natural multiscale systems such as cellulose-based plant and wood materials. An important trait of these materials is that they display distinctive hierarchical structures across multiple scales, where molecular details are exhibited in macroscale mechanical responses. Protein materials are intriguing examples of materials that balance multiple tasks, representing some of the most sustainable material solutions that integrate structure and function despite severe limitations in the quality and quantity of material building blocks. However, up until now, our attempts to analyze and replicate Nature’s materials have been hindered by our lack of fundamental understanding of these materials’ intricate hierarchical structures, scale-bridging mechanisms, and complex material components that bestow protein-based materials their unique properties. Recent advances in analytical tools and experimental methods allow a holistic view of such a hierarchical biological material system. The integration of these approaches and amalgamation of material properties at all scale levels to develop a complete description of a material system falls within the emerging field of materiomics. Materiomics is the result of the convergence of engineering and materials science with experimental and computational biology in the context of natural and synthetic materials. Through materiomics, fundamental advances in our understanding of structure–property–process relations of biological systems contribute to the mechanistic understanding of certain diseases and facilitate the development of novel biological, biologically inspired, and completely synthetic materials for applications in medicine (biomaterials), nanotechnology, and engineering. PMID:24198478

Growth Mechanism of Pumpkin-Shaped Vaterite Hierarchical Structures

NASA Astrophysics Data System (ADS)

Ma, Guobin; Xu, Yifei; Wang, Mu

2015-03-01

CaCO3-based biominerals possess sophisticated hierarchical structures and promising mechanical properties. Recent researches imply that vaterite may play an important role in formation of CaCO3-based biominerals. However, as a less common polymorph of CaCO3, the growth mechanism of vaterite remains not very clear. Here we report the growth of a pumpkin-shaped vaterite hierarchical structure with a six-fold symmetrical axis and lamellar microstructure. We demonstrate that the growth is controlled by supersaturation and the intrinsic crystallographic anisotropy of vaterite. For the scenario of high supersaturation, the nucleation rate is higher than the lateral extension rate, favoring the ``double-leaf'' spherulitic growth. Meanwhile, nucleation occurs preferentially in < 11 2 0 > as determined by the crystalline structure of vaterite, modulating the grown products with a hexagonal symmetry. The results are beneficial for an in-depth understanding of the biomineralization of CaCO3. The growth mechanism may also be applicable to interpret the formation of similar hierarchical structures of other materials. The authors gratefully acknowledge the financial support from National Science Foundation of China (Grant Nos. 51172104 and 50972057) and National Key Basic Research Program of China (Grant No. 2010CB630705).

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality.

PubMed

Fujita, Takeshi

2017-01-01

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

PubMed Central

Fujita, Takeshi

2017-01-01

Abstract Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals. PMID:29057026

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

NASA Astrophysics Data System (ADS)

Fujita, Takeshi

2017-12-01

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.

Mathematical Methods of System Analysis in Construction Materials

NASA Astrophysics Data System (ADS)

Garkina, Irina; Danilov, Alexander

2017-10-01

System attributes of construction materials are defined: complexity of an object, integrity of set of elements, existence of essential, stable relations between elements defining integrative properties of system, existence of structure, etc. On the basis of cognitive modelling (intensive and extensive properties; the operating parameters) materials (as difficult systems) and creation of the cognitive map the hierarchical modular structure of criteria of quality is under construction. It actually is a basis for preparation of the specification on development of material (the required organization and properties). Proceeding from a modern paradigm (model of statement of problems and their decisions) of development of materials, levels and modules are specified in structure of material. It when using the principles of the system analysis allows to considered technological process as the difficult system consisting of elements of the distinguished specification level: from atomic before separate process. Each element of system depending on an effective objective is considered as separate system with more detailed levels of decomposition. Among them, semantic and qualitative analyses of an object (are considered a research objective, decomposition levels, separate elements and communications between them come to light). Further formalization of the available knowledge in the form of mathematical models (structural identification) is carried out; communications between input and output parameters (parametrical identification) are defined. Hierarchical structures of criteria of quality are under construction for each allocated level. On her the relevant hierarchical structures of system (material) are under construction. Regularities of structurization and formation of properties, generally are considered at the levels from micro to a macrostructure. The mathematical model of material is represented as set of the models corresponding to private criteria by which separate modules and their levels (the mathematical description, a decision algorithm) are defined. Adequacy is established (compliance of results of modelling to experimental data; is defined by the level of knowledge of process and validity of the accepted assumptions). The global criterion of quality of material is considered as a set of private criteria (properties). Synthesis of material is carried out on the basis of one-criteria optimization on each of the chosen private criteria. Results of one-criteria optimization are used at multicriteria optimization. The methods of developing materials as single-purpose, multi-purpose, including contradictory, systems are indicated. The scheme of synthesis of composite materials as difficult systems is developed. The specified system approach effectively was used in case of synthesis of composite materials with special properties.

Hierarchically-structured hollow NiO nanospheres/nitrogen-doped graphene hybrid with superior capacity retention and enhanced rate capability for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Chen, Jiayuan; Wu, Xiaofeng; Liu, Ya; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Tan, Qiangqiang; Chen, Yunfa

2017-12-01

A facile template-free synthesis strategy is demonstrated to fabricate nanostructured NiO/N-doped graphene hybrid, in which NiO hollow nanospheres with hierarchically mesoporous structure are tightly anchored on N-doped graphene matrix. The mesoporous shell of NiO can not only provide sufficient electrode/electrolyte contact areas to accelerate ion diffusion and electron exchange, but also efficiently mitigate the volume change that occurs during long-time reactions. Simultaneously, the reduced graphene oxide with doping nitrogen atoms are employed as effectively conductive backbone, further enhancing the electrochemical performances. When used as anodic material for lithium ion batteries, the synergistic system delivers a reversible capacity up to 1104.6 mAh g-1 after 150 cycles at a current density of 0.08 A g-1 and 422.3 mAh g-1 at a high charging rate of 4 A g-1, which is better than those of the bare counterparts and most other NiO-based materials reported in the previous literatures. The hierarchically hollow NiO nanostructure combined with N-doped graphene matrix provides a promising candidate applied in advanced anode materials for lithium ion batteries.

Construction of a Hierarchical Architecture of Covalent Organic Frameworks via a Postsynthetic Approach.

PubMed

Zhang, Gen; Tsujimoto, Masahiko; Packwood, Daniel; Duong, Nghia Tuan; Nishiyama, Yusuke; Kadota, Kentaro; Kitagawa, Susumu; Horike, Satoshi

2018-02-21

Covalent organic frameworks (COFs) represent an emerging class of crystalline porous materials that are constructed by the assembly of organic building blocks linked via covalent bonds. Several strategies have been developed for the construction of new COF structures; however, a facile approach to fabricate hierarchical COF architectures with controlled domain structures remains a significant challenge, and has not yet been achieved. In this study, a dynamic covalent chemistry (DCC)-based postsynthetic approach was employed at the solid-liquid interface to construct such structures. Two-dimensional imine-bonded COFs having different aromatic groups were prepared, and a homogeneously mixed-linker structure and a heterogeneously core-shell hollow structure were fabricated by controlling the reactivity of the postsynthetic reactions. Solid-state nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) confirmed the structures. COFs prepared by a postsynthetic approach exhibit several functional advantages compared with their parent phases. Their Brunauer-Emmett-Teller (BET) surface areas are 2-fold greater than those of their parent phases because of the higher crystallinity. In addition, the hydrophilicity of the material and the stepwise adsorption isotherms of H 2 O vapor in the hierarchical frameworks were precisely controlled, which was feasible because of the distribution of various domains of the two COFs by controlling the postsynthetic reaction. The approach opens new routes for constructing COF architectures with functionalities that are not possible in a single phase.

High energy density and efficiency achieved in nanocomposite film capacitors via structure modulation

NASA Astrophysics Data System (ADS)

Zeng, Yi; Shen, Zhong-Hui; Shen, Yang; Lin, Yuanhua; Nan, Ce-Wen

2018-03-01

Flexible dielectric polymer films with high energy storage density and high charge-discharge efficiency have been considered as promising materials for electrical power applications. Here, we design hierarchical structured nanocomposite films using nonlinear polymer poly(vinylidene fluoride-HFP) [P(VDF-HFP)] with inorganic h-boron nitride (h-BN) nanosheets by electrospinning and hot-pressing methods. Our results show that the addition of h-BN nanosheets and the design of the hierarchical multilayer structure in the nanocomposites can remarkably enhance the charge-discharge efficiency and energy density. A high charge-discharge efficiency of 78% and an energy density of 21 J/cm3 can be realized in the 12-layered PVDF/h-BN nanocomposite films. Phase-field simulation results reveal that the spatial distribution of the electric field in these hierarchical structured films affects the charge-discharge efficiency and energy density. This work provides a feasible route, i.e., structure modulation, to improve the energy storage performances for nanocomposite films.

Self-assembled materials and supramolecular chemistry within microfluidic environments: from common thermodynamic states to non-equilibrium structures.

PubMed

Sevim, S; Sorrenti, A; Franco, C; Furukawa, S; Pané, S; deMello, A J; Puigmartí-Luis, J

2018-05-01

Self-assembly is a crucial component in the bottom-up fabrication of hierarchical supramolecular structures and advanced functional materials. Control has traditionally relied on the use of encoded building blocks bearing suitable moieties for recognition and interaction, with targeting of the thermodynamic equilibrium state. On the other hand, nature leverages the control of reaction-diffusion processes to create hierarchically organized materials with surprisingly complex biological functions. Indeed, under non-equilibrium conditions (kinetic control), the spatio-temporal command of chemical gradients and reactant mixing during self-assembly (the creation of non-uniform chemical environments for example) can strongly affect the outcome of the self-assembly process. This directly enables a precise control over material properties and functions. In this tutorial review, we show how the unique physical conditions offered by microfluidic technologies can be advantageously used to control the self-assembly of materials and of supramolecular aggregates in solution, making possible the isolation of intermediate states and unprecedented non-equilibrium structures, as well as the emergence of novel functions. Selected examples from the literature will be used to confirm that microfluidic devices are an invaluable toolbox technology for unveiling, understanding and steering self-assembly pathways to desired structures, properties and functions, as well as advanced processing tools for device fabrication and integration.

Controlling macro- and mesostructures with hierarchical porosity through combined hard and soft templating.

PubMed

Petkovich, Nicholas D; Stein, Andreas

2013-05-07

Rigid, porous objects and surfactants serve as powerful templates for the formation of mesoporous and macroporous materials. When both types of template are combined in a single synthesis, materials with intricate architectures and hierarchical porosity can be obtained. In this tutorial review, we explain how to conduct syntheses with both soft and hard templates; moreover, we describe methods to control the final structure present in the templated material. Much of the foundation for multiple templating lies in the study of materials made with only one type of template. To establish a foundation in this area, a description of hard and soft templating is given, delving into the templates available and the steps required for effective templating. This leads into an extended discussion about materials templated with both hard and soft templates. Through the use of recent examples in the literature, we aim to show the diversity of structures possible through multiple templating and the advantages these structures can provide for a wide range of applications. An emphasis is placed on how various factors-such as the type of template, type of precursor, heat-treatment temperature, confinement within a small space, and template-template interactions-impact morphology.

Hierarchical Micro/Nano Structures by Combined Self-Organized Dewetting and Photopatterning of Photoresist Thin Films.

PubMed

Sachan, Priyanka; Kulkarni, Manish; Sharma, Ashutosh

2015-11-17

Photoresists are the materials of choice for micro/nanopatterning and device fabrication but are rarely used as a self-assembly material. We report for the first time a novel interplay of self-assembly and photolithography for fabrication of hierarchical and ordered micro/nano structures. We create self-organized structures by the intensified dewetting of unstable thin (∼10 nm to 1 μm) photoresist films by annealing them in an optimal solvent and nonsolvent liquid mixture that allows spontaneous dewetting to form micro/nano smooth dome-like structures. The density, size (∼100 nm to millimeters), and curvature/contact angle of the dome/droplet structures are controlled by the film thickness, composition of the dewetting liquid, and time of annealing. Ordered dewetted structures are obtained simply by creating spatial variation of viscosity by ultraviolet exposure or by photopatterning before dewetting. Further, the structures thus fabricated are readily photopatterned again on the finer length scales after dewetting. We illustrate the approach by fabricating several three-dimensional structures of varying complexity with secondary and tertiary features.

Electrospun mulberry-like hierarchical carbon fiber web for high-performance supercapacitors.

PubMed

Liu, Chao; Liu, Jizi; Wang, Jing; Li, Jiansheng; Luo, Rui; Shen, Jinyou; Sun, Xiuyun; Han, Weiqing; Wang, Lianjun

2018-02-15

In this work, we have fabricated a kind of N-doped hierarchal carbon fiber web by electrospinning hollow mesoporous carbon spheres (HMCSs) into fibrous structure. The as-synthesized carbon fiber web with novel mulberry-like morphology, thus denoted as MC-FW, possesses micro/meso/macroporous porosity, large surface area, high conductivity and multi-level structure, which are highly desired for supercapacitor electrode materials. The electrochemical measurements demonstrate that the designed MC-FW shows high capacitance (298.6 F g -1 ), favorable capacitance retention (71.0%) and long cycle life (97.3% capacitance retention after 5000 cycles). Notably, the capacitance of 298.6 F g -1 for MC-FW is higher than the capacitance reported so far for many hollow carbon spheres and carbon fibers, which may contribute to the synergistic effect between the merits of HMCSs (e.g. micro/meso/macroporous hierarchal structure, large surface area, high pore volume) and advantages of 1D carbon fiber (e.g. large aspect ratio and high conductivity). It is believed that this distinctive carbon fiber web may show promising prospects as advanced energy storage materials and catalyst. Copyright © 2017 Elsevier Inc. All rights reserved.

Fabrication of hierarchical porous nickel based metal-organic framework (Ni-MOF) constructed with nanosheets as novel pseudo-capacitive material for asymmetric supercapacitor.

PubMed

Du, Pengcheng; Dong, Yuman; Liu, Chang; Wei, Wenli; Liu, Dong; Liu, Peng

2018-05-15

Hierarchical porous nickel based metal-organic framework (Ni-MOF) constructed with nanosheets is fabricated by a facile hydrothermal process with the existence of trimesic acid and nickel ions. Various structures of Ni-MOFs can be obtained through adjusting the molar ratio of trimesic acid and nickel ion, the obtained hierarchical porous Ni-MOF exhibits optimal porous structure, which also possesses largest specific surface area. The hierarchical porous structure constructed with nanosheets can supply more active sites for electrochemical reactions to realize the excellent electrochemical properties, thus the hierarchical porous Ni-MOF reveals an outstanding specific capacitance of 1057 F/g at current density of 1 A/g, and delivers high specific capacitance of 649 F/g at current density of 30 A/g, indicating that it exhibits good rate capability of 63.4% even up to 30 A/g. The hierarchical porous Ni-MOF keeps 70% of its original value up to 2 500 charge-discharge cycles at the current density of 10 A/g. Furthermore, asymmetric supercapacitors (ASCs) were assembled based on hierarchical porous Ni-MOF and activated carbon (AC), the ASCs reveal specific capacitance of 87 F/g at current density of 0.5 A/g, and exhibit high energy density of 21.05 Wh/kg and power density of 6.03 kW/kg. Additionally, the tandem ASCs can light up a red LED. The hierarchical porous Ni-MOF exhibits promising applications in high performance supercapacitors. Copyright © 2018 Elsevier Inc. All rights reserved.

Graphene-Like 2D Porous Carbon Nanosheets Derived from Cornstalk Pith for Energy Storage Materials

NASA Astrophysics Data System (ADS)

Gao, Kezheng; Niu, Qingyuan; Tang, Qiheng; Guo, Yaqing; Wang, Lizhen

2018-01-01

Biomass materials from different organisms or different parts (even different periods) of the same organism have different microscopic morphologies, hierarchical pore structures and even elemental compositions. Therefore, carbon materials inheriting the unique hierarchical microstructure of different biomass materials may exhibit significantly different electrochemical properties. Cornstalk pith and cornstalk skin (dried by freeze-drying) exhibit significantly different microstructures due to their different biological functions. The cornstalk skin-based carbon (S-carbon) exhibits a thick planar morphology, and the Barrett-Emmett-Teller (BET) surface area is only about 332.07 m2 g-1. However, cornstalk pith-based carbon (P-carbon) exhibits a graphene-like 2D porous nanosheet structure with a rough, wrinkled morphology, and the BET surface area is about 805.17 m2 g-1. In addition, a P-carbon supercapacitor exhibits much higher specific capacitance and much better rate capability than an S-carbon supercapacitor in 6 M potassium hydroxide (KOH) electrolyte.

Inward Lithium-Ion Breathing of Hierarchically Porous Silicon Anodes

DOE PAGES

Xiao, Qiangfeng; Gu, Meng; Yang, Hui; ...

2015-11-05

Silicon has been identified as one of the most promising candidates as anode for high performance lithium-ion batteries. The key challenge for Si anodes is the large volume change induced chemomechanical fracture and subsequent rapid capacity fading upon cyclic charge and discharge. Improving capacity retention thus critically relies on smart accommodation of the volume changes through nanoscale structural design. In this work, we report a novel fabrication method for hierarchically porous Si nanospheres (hp-SiNSs), which consist of a porous shell and a hollow core. Upon charge/discharge cycling, the hp-SiNSs accommodate the volume change through reversible inward expansion/contraction with negligible particle-levelmore » outward expansion. Our mechanics analysis revealed that such a unique volume-change accommodation mechanism is enabled by the much stiffer modulus of the lithiated layer than the unlithiated porous layer and the low flow stress of the porous structure. Such inward expansion shields the hp-SiNSs from fracture, opposite to the outward expansion in solid Si during lithiation. Lithium ion battery assembled with this new nanoporous material exhibits high capacity, high power, long cycle life and high coulombic efficiency, which is superior to the current commercial Si-based anode materials. We find the low cost synthesis approach reported here provides a new avenue for the rational design of hierarchically porous structures with unique materials properties.« less

Three-dimensional hierarchical and interconnected honeycomb-like porous carbon derived from pomelo peel for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Jingyuan; Li, Hongpeng; Zhang, Hongsen; Liu, Qi; Li, Rumin; Li, Bin; Wang, Jun

2018-01-01

The urgent need for sustainable development of human society has forced material scientists to explore novel materials starting from cheap natural precursors for next-generation energy storage devices by using environmentally friendly strategies. In this work, heteroatom-functionalized porous carbonaceous materials with 3D hierarchical and interconnected honeycomb-like structure have been successfully synthesized by using waste biomass pomelo peel as raw material through the combination of hydrothermal carbonization and followed KOH activation procedure. Benefiting from the unique honeycomb-like structure and high specific surface area, the as-obtained carbon material exhibits satisfactory capacitive behavior: 374 F/g at 0.1 A/g; excellent cycling stability of 92.5% capacitance retention over continuous 5000 cycles. More importantly, the as-assembled symmetric supercapacitors based on as-prepared electrode material can deliver high gravimetric and volumetric energy density of 20 W h/kg and 18.7 W h/L in 6 M KOH, respectively, as well as outstanding cycling stability. The obtained results demonstrate the possibility for taking full advantage of sustainable and large scale advanced carbon materials by choosing waste biomass, particularly the pomelo peel as a raw material.

Hierarchically structured activated carbon for ultracapacitors

NASA Astrophysics Data System (ADS)

Kim, Mok-Hwa; Kim, Kwang-Bum; Park, Sun-Min; Roh, Kwang Chul

2016-02-01

To resolve the pore-associated bottleneck problem observed in the electrode materials used for ultracapacitors, which inhibits the transport of the electrolyte ions, we designed hierarchically structured activated carbon (HAC) by synthesizing a mesoporous silica template/carbon composite and chemically activating it to simultaneously remove the silica template and increase the pore volume. The resulting HAC had a well-designed, unique porous structure, which allowed for large interfaces for efficient electric double-layer formation. Given the unique characteristics of the HAC, we believe that the developed synthesis strategy provides important insights into the design and fabrication of hierarchical carbon nanostructures. The HAC, which had a specific surface area of 1,957 m2 g-1, exhibited an extremely high specific capacitance of 157 F g-1 (95 F cc-1), as well as a high rate capability. This indicated that it had superior energy storage capability and was thus suitable for use in advanced ultracapacitors.

The well-designed hierarchical structure of Musa basjoo for supercapacitors

PubMed Central

Zheng, Kaiwen; Fan, Xiaorong; Mao, Yingzhu; Lin, Jingkai; Dai, Wenxuan; Zhang, Junying; Cheng, Jue

2016-01-01

Application of biological structure is one of the hottest topics in the field of science and technology. The unimaginable and excellent architectures of living beings supporting their vital activities have attracted the interests of worldwide researchers. An intriguing example is Musa basjoo which belongs to the herb, while appears like a tree. The profound mystery of structure and potential application of Musa basjoo have not been probed. Here we show the finding of the hierarchical structure of Musa basjoo and the outstanding electrochemical performance of the super-capacitors fabricated through the simple carbonization of Musa basjoo followed by KOH activation. Musa basjoo has three layers of structure: nanometer-level, micrometer-level and millimeter-level. The nanometer-level structure constructs the micrometer-level structure, while the micrometer-level structure constructs the millimeter-level structure. Based on this hierarchical structure, Musa basjoo reduces the unnecessary weight and therefore supports its huge body. The super-capacitors derived from Musa basjoo display a high specific capacitance and a good cycling stability. This enlightening work opens a window for the applications of the natural structure and we hope that more and more people could pay attention to the bio-inspired materials. PMID:26842714

The well-designed hierarchical structure of Musa basjoo for supercapacitors.

PubMed

Zheng, Kaiwen; Fan, Xiaorong; Mao, Yingzhu; Lin, Jingkai; Dai, Wenxuan; Zhang, Junying; Cheng, Jue

2016-02-04

Application of biological structure is one of the hottest topics in the field of science and technology. The unimaginable and excellent architectures of living beings supporting their vital activities have attracted the interests of worldwide researchers. An intriguing example is Musa basjoo which belongs to the herb, while appears like a tree. The profound mystery of structure and potential application of Musa basjoo have not been probed. Here we show the finding of the hierarchical structure of Musa basjoo and the outstanding electrochemical performance of the super-capacitors fabricated through the simple carbonization of Musa basjoo followed by KOH activation. Musa basjoo has three layers of structure: nanometer-level, micrometer-level and millimeter-level. The nanometer-level structure constructs the micrometer-level structure, while the micrometer-level structure constructs the millimeter-level structure. Based on this hierarchical structure, Musa basjoo reduces the unnecessary weight and therefore supports its huge body. The super-capacitors derived from Musa basjoo display a high specific capacitance and a good cycling stability. This enlightening work opens a window for the applications of the natural structure and we hope that more and more people could pay attention to the bio-inspired materials.

The well-designed hierarchical structure of Musa basjoo for supercapacitors

NASA Astrophysics Data System (ADS)

Zheng, Kaiwen; Fan, Xiaorong; Mao, Yingzhu; Lin, Jingkai; Dai, Wenxuan; Zhang, Junying; Cheng, Jue

2016-02-01

Application of biological structure is one of the hottest topics in the field of science and technology. The unimaginable and excellent architectures of living beings supporting their vital activities have attracted the interests of worldwide researchers. An intriguing example is Musa basjoo which belongs to the herb, while appears like a tree. The profound mystery of structure and potential application of Musa basjoo have not been probed. Here we show the finding of the hierarchical structure of Musa basjoo and the outstanding electrochemical performance of the super-capacitors fabricated through the simple carbonization of Musa basjoo followed by KOH activation. Musa basjoo has three layers of structure: nanometer-level, micrometer-level and millimeter-level. The nanometer-level structure constructs the micrometer-level structure, while the micrometer-level structure constructs the millimeter-level structure. Based on this hierarchical structure, Musa basjoo reduces the unnecessary weight and therefore supports its huge body. The super-capacitors derived from Musa basjoo display a high specific capacitance and a good cycling stability. This enlightening work opens a window for the applications of the natural structure and we hope that more and more people could pay attention to the bio-inspired materials.

Fabricating hierarchically porous carbon with well-defined open pores via polymer dehalogenation for high-performance supercapacitor

NASA Astrophysics Data System (ADS)

Guo, Mei; Li, Yu; Du, Kewen; Qiu, Chaochao; Dou, Gang; Zhang, Guoxin

2018-05-01

Improving specific energy of supercapacitors (SCs) at high power has been intensively investigated as a hot and challengeable topic. In this work, hierarchically porous carbon (HPC) materials with well-defined meso-/macro-pores are reported via the dehalogenation reaction of polyvinyl fluoride (PVDF) by NaNH2. The pore hierarchy is achievable mainly because of the coupled effects of NaNH2 activation and the template/bubbling effects of byproducts of NaF and NH3. Electron microscopy studies and Brunauer-Emmett-Teller (BET) measurements confirm that the structures of HPC samples contain multiple-scale pores assembled in a hierarchical pattern, and most of their volumes are contributed by mesopores. Aqueous symmetric supercapacitors (ASSCs) were fabricated using HPC-M7 materials, achieving an ultrahigh specific energy of 18.8 Wh kg-1 at specific power of 986.8 W kg-1. Remarkably, at the ultrahigh power of 14.3 kW kg-1, the HPC-ASSCs still output a very high specific energy of 16.7 Wh kg-1, which means the ASSCs can be charged or discharged within 4 s. The outstanding rate capacitive performance is mainly benefited from the hierarchical porous structure that allows highly efficient ion diffusion.

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

A facile approach toward transition metal oxide hierarchical structures and their lithium storage properties.

PubMed

Zhang, Cuimiao; Chen, Jing; Zeng, Yi; Rui, Xianhong; Zhu, Jixin; Zhang, Wenyu; Xu, Chen; Lim, Tuti Mariana; Hng, Huey Hoon; Yan, Qingyu

2012-06-21

A simple, non-template, non-surfactant and environmentally friendly hydrothermal method is presented based on the controlled release of the reactants into the reaction solvents to induce slow nucleation and growth of three-dimensional hierarchical nanostructures of transition metal oxides. This method is a general approach, which can be used to prepare Co(3)O(4), CuO, and Ni(OH)(2)/NiO. These metal oxides with hierarchical nanostructures can be used as anode materials for lithium-ion batteries with good Li storage performance, e.g. high specific capacities and stable cyclability.

Patterned Diblock Co-Polymer Thin Films as Templates for Advanced Anisotropic Metal Nanostructures.

PubMed

Roth, Stephan V; Santoro, Gonzalo; Risch, Johannes F H; Yu, Shun; Schwartzkopf, Matthias; Boese, Torsten; Döhrmann, Ralph; Zhang, Peng; Besner, Bastian; Bremer, Philipp; Rukser, Dieter; Rübhausen, Michael A; Terrill, Nick J; Staniec, Paul A; Yao, Yuan; Metwalli, Ezzeldin; Müller-Buschbaum, Peter

2015-06-17

We demonstrate glancing-angle deposition of gold on a nanostructured diblock copolymer, namely polystyrene-block-poly(methyl methacrylate) thin film. Exploiting the selective wetting of gold on the polystyrene block, we are able to fabricate directional hierarchical structures. We prove the asymmetric growth of the gold nanoparticles and are able to extract the different growth laws by in situ scattering methods. The optical anisotropy of these hierarchical hybrid materials is further probed by angular resolved spectroscopic methods. This approach enables us to tailor functional hierarchical layers in nanodevices, such as nanoantennae arrays, organic photovoltaics, and sensor electronics.

Controllable synthesis of mesoporous multi-shelled ZnO microspheres as efficient photocatalysts for NO oxidation

NASA Astrophysics Data System (ADS)

Chen, Xiaolang; Zhang, Huiqiang; Zhang, Dieqing; Miao, Yingchun; Li, Guisheng

2018-03-01

The successful application of hierarchically porous structure in environmental treatment has provided new insights for solving environmental problems. Hierarchically structured semiconductor materials were considered as promising photocatalysts for NO oxidation in gas phase. Multi-shelled ZnO microspheres (MMSZ) were controllably shaped with hierarchically porous structures via a facile hydrothermal route using amino acid (N-Acetyl-D-Proline) as template and post-calcination treatment. Symmetric Ostwald ripening was used to explain the morphological evolution of hierarchical nanostructure. MMSZ was proved highly efficient for oxidizing NO (400 ppb) in gas phase under UV light irradiation with a much higher photocatalytic removal rate (77.3%) than that of the as-obtained ZnO crystals with other hierachically porous structures, owing to its higher photocurrent intensity. Such greatly enhanced photocatalytic activity can be assigned to the enhanced crystallinity of ZnO, mesopores and unique multi-shelled structure. Enhanced crystallinity promotes photogenerated charges under light irradiation. Mesoporous porosity can ensure enough light scattering between the shells. Multi-shelled structure endows ZnO with higher specific surface area and high frequency of multiple light reflection, resulting in more exposed active sites, higher light utilization efficiency, and fast separation efficiency of photogenerated charge carriers. The experimental results demonstrated that the photogenerated holes (h+) are the main active species. Hierarchically structured ZnO is not only contributed to directly use solar energy to solving various problems caused by atmospheric pollution, but also has potential applications in energy converse and storage including solar cells, lithium batteries, water-splitting, etc.

Preparation and properties of ZnS superhydrophobic surface with hierarchical structure

NASA Astrophysics Data System (ADS)

Yao, Lujun; Zheng, Maojun; He, Shuanghu; Ma, Li; Li, Mei; Shen, Wenzhong

2011-01-01

A novel ZnS hierarchical structure composed of nanorod arrays with branched nanosheets and nanowires grown on their upside walls, was synthesized over Au-coated silicon substrate via chemical vapor deposition technique. Contact angle and sliding angle of this hierarchical film with no surface modification were measured to be about 153.8° and 9.1° for 5 μl water droplets. Self-cleaning behavior and dynamic water-repelling performance were clearly demonstrated. In addition, electrowetting transition phenomenon from superhydrophobic to hydrophilic state happened when a critical bias ∼7.0 V was applied. Below this threshold voltage, the contact angle change is little. This work for the first time reports the creation of ZnS superhydrophobic surface and could enrich its research field as surface functional materials.

Resolving the Framework Position of Organic Structure-Directing Agents in Hierarchical Zeolites via Polarized Stimulated Raman Scattering.

PubMed

Fleury, Guillaume; Steele, Julian A; Gerber, Iann C; Jolibois, F; Puech, P; Muraoka, Koki; Keoh, Sye Hoe; Chaikittisilp, Watcharop; Okubo, Tatsuya; Roeffaers, Maarten B J

2018-04-05

The direct synthesis of hierarchically intergrown silicalite-1 can be achieved using a specific diquaternary ammonium agent. However, the location of these molecules in the zeolite framework, which is critical to understand the formation of the material, remains unclear. Where traditional characterization tools have previously failed, herein we use polarized stimulated Raman scattering (SRS) microscopy to resolve molecular organization inside few-micron-sized crystals. Through a combination of experiment and first-principles calculations, our investigation reveals the preferential location of the templating agent inside the linear pores of the MFI framework. Besides illustrating the attractiveness of SRS microscopy in the field of material science to study and spatially resolve local molecular distribution as well as orientation, these results can be exploited in the design of new templating agents for the preparation of hierarchical zeolites.

Synthesis of Hierarchically Porous Sandwich-Like Carbon Materials for High-Performance Supercapacitors.

PubMed

Li, Yiju; Chen, Chaoji; Gao, Tingting; Zhang, Dongming; Huang, Xiaomei; Pan, Yue; Ye, Ke; Cheng, Kui; Cao, Dianxue; Wang, Guiling

2016-11-14

For the first time, hierarchically porous carbon materials with a sandwich-like structure are synthesized through a facile and efficient tri-template approach. The hierarchically porous microstructures consist of abundant macropores and numerous micropores embedded into the crosslinked mesoporous walls. As a result, the obtained carbon material with a unique sandwich-like structure has a relatively high specific surface (1235 m 2  g -1 ), large pore volume (1.30 cm 3  g -1 ), and appropriate pore size distribution. These merits lead to a comparably high specific capacitance of 274.8 F g -1 at 0.2 A g -1 and satisfying rate performance (87.7 % retention from 1 to 20 A g -1 ). More importantly, the symmetric supercapacitor with two identical as-prepared carbon samples shows a superior energy density of 18.47 Wh kg -1 at a power density of 179.9 W kg -1 . The asymmetric supercapacitor based on as-obtained carbon sample and its composite with manganese dioxide (MnO 2 ) can reach up to an energy density of 25.93 Wh kg -1 at a power density of 199.9 W kg -1 . Therefore, these unique carbon material open a promising prospect for future development and utilization in the field of energy storage. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of 1D Hierarchical Material Mesosilica/Pal Composite and Its Performance in the Adsorption of Methyl Orange

PubMed Central

Wu, Mei; Han, Haifeng; Ni, Lingli; Song, Daiyun; Li, Shuang; Hu, Tao; Jiang, Jinlong; Chen, Jing

2018-01-01

This paper highlights the synthesis of a one-dimensional (1D) hierarchical material mesosilica/palygorskite (Pal) composite and evaluates its adsorption performance for anionic dye methyl orange (MO) in comparison with Pal and Mobile crystalline material-41 (MCM-41). The Mesosilica/Pal composite is consisted of mesosilica coated Pal nanorods and prepared through a dual template approach using cetyltrimethyl ammonium bromide (CTAB) and Pal as soft and hard templates, respectively. The composition and structure of the resultant material was characterized by a scanning electron microscope (SEM), transmissionelectron microscopy (TEM), N2 adsorption-desorption analysis, small-angle X-Ray powder diffraction (XRD), and zeta potential measurement. Adsorption experiments were carried out with different absorbents at different contact times and pH levels. Compared with Pal and MCM-41, the mesosilica/Pal composite exhibited the best efficiency for MO adsorption. Its adsorption ratio is as high as 70.4%. Its adsorption equilibrium time is as short as 30 min. Results testify that the MO retention is promoted for the micro-mesoporous hierarchical structure and positive surface charge electrostatic interactions of the mesosilica/Pal composite. The regenerability of the mesosilica/Pal composite absorbent was also assessed. 1D morphology makes it facile to separate from aqueous solutions. It can be effortlessly recovered and reused for up to nine cycles. PMID:29361713

Preparation of 1D Hierarchical Material Mesosilica/Pal Composite and Its Performance in the Adsorption of Methyl Orange.

PubMed

Wu, Mei; Han, Haifeng; Ni, Lingli; Song, Daiyun; Li, Shuang; Hu, Tao; Jiang, Jinlong; Chen, Jing

2018-01-20

This paper highlights the synthesis of a one-dimensional (1D) hierarchical material mesosilica/palygorskite (Pal) composite and evaluates its adsorption performance for anionic dye methyl orange (MO) in comparison with Pal and Mobile crystalline material-41 (MCM-41). The Mesosilica/Pal composite is consisted of mesosilica coated Pal nanorods and prepared through a dual template approach using cetyltrimethyl ammonium bromide (CTAB) and Pal as soft and hard templates, respectively. The composition and structure of the resultant material was characterized by a scanning electron microscope (SEM), transmissionelectron microscopy (TEM), N₂ adsorption-desorption analysis, small-angle X-Ray powder diffraction (XRD), and zeta potential measurement. Adsorption experiments were carried out with different absorbents at different contact times and pH levels. Compared with Pal and MCM-41, the mesosilica/Pal composite exhibited the best efficiency for MO adsorption. Its adsorption ratio is as high as 70.4%. Its adsorption equilibrium time is as short as 30 min. Results testify that the MO retention is promoted for the micro-mesoporous hierarchical structure and positive surface charge electrostatic interactions of the mesosilica/Pal composite. The regenerability of the mesosilica/Pal composite absorbent was also assessed. 1D morphology makes it facile to separate from aqueous solutions. It can be effortlessly recovered and reused for up to nine cycles.

Hierarchical flower-like C/NiO composite hollow microspheres and its excellent supercapacitor performance

NASA Astrophysics Data System (ADS)

Liu, Tao; Jiang, Chuanjia; Cheng, Bei; You, Wei; Yu, Jiaguo

2017-08-01

Nickel (II) oxide (NiO) nanosheet grown on N-doped carbon hollow spheres (NiO/NCHS) with hierarchical pore structure are obtained via facile chemical bath deposition followed by calcination at 350 °C under nitrogen atmosphere. Phase structure measurements indicate that the material is composed of NiO and N-doped carbon. The NiO/NCHS composite exhibits a unique flower-like morphology, where ultrathin NiO nanosheets are vertically grown on the surface of NCHS. This hierarchical nanostructure is beneficial for facilitating electron and electrolyte ion transport and accelerating the reversible redox reaction. The specific capacitance of the NiO/NCHS composite (585 F g-1 at 1 A g-1) is higher than that of pure NiO particle (453 F g-1 at 1 A g-1). Meanwhile, the NiO/NCHS composite exhibits excellent rate performance and superior cycling stability over 6000 cycles. The enhanced supercapacitive performance of the NiO/NCHS nanocomposite indicates that it can be an appealing candidate electrode material for supercapacitors.

Efficient Gas-Sensing for Formaldehyde with 3D Hierarchical Co3O4 Derived from Co5-Based MOF Microcrystals.

PubMed

Zhou, Wei; Wu, Ya-Pan; Zhao, Jun; Dong, Wen-Wen; Qiao, Xiu-Qing; Hou, Dong-Fang; Bu, Xianhui; Li, Dong-Sheng

2017-11-20

Detecting formaldehyde at low operating temperature and maintaining long-term stability are of great significance. In this work, a hierarchical Co 3 O 4 nanostructure has been fabricated by calcining Co 5 -based metal-organic framework (MOF) microcrystals. Co 3 O 4 -350 particles were used for efficient gas-sensing for the detecting of formaldehyde vapor at lower working temperature (170 °C), low detection limit of 10 ppm, and long-term stability (30 days), which not only is the optimal value among all reported pure Co 3 O 4 sensing materials for the detection of formaldehyde but also is superior to that of majority of Co 3 O 4 -based composites. Such extraordinarily efficient properties might be resulted from hierarchically structures, larger surface area and unique pore structure. This strategy is further confirmed that MOFs, especially Co-clusters MOFs, could be used as precursor to synthesize 3D nanostructure metal oxide materials with high-performance, which possess high porosity and more active sites and shorter ionic diffusion lengths.

Hierarchical honeycomb-like Co3O4 pores coating on CoMoO4 nanosheets as bifunctional efficient electrocatalysts for overall water splitting

NASA Astrophysics Data System (ADS)

Pei, Zhihao; Xu, Li; Xu, Wei

2018-03-01

Efficient electrocatalytic water splitting is one of the most effective ways to solve the global energy crisis. In this paper, we report on a novel self-assembled hierarchical structure of Co3O4/CoMoO4 grown in situ on a bare nickel foam. The unique, three-dimensional honeycomb-like Co3O4 pores were constructed from one-dimensional nanowires and coated on two-dimensional CoMoO4 nanosheets structures grown on nickel foam. The synthesis involved a step-wise solvothermal method followed by an annealing treatment. Benefiting from the synergistic effect of the hierarchical nanostructures, the materials had more reaction active sites and a smaller electron transfer impedance, and they exhibited excellent electrocatalytic performances for the HER and OER of 143 and 244 mV, respectively, at 10 mA cm-2 in an alkaline solution. Furthermore, the materials remained stable during the long electrolysis period, over 10 h, presenting promising application prospects in the field of electrocatalytic water splitting.

Bioinspired Carbon/SnO2 Composite Anodes Prepared from a Photonic Hierarchical Structure for Lithium Batteries.

PubMed

Li, Yao; Meng, Qing; Ma, Jun; Zhu, Chengling; Cui, Jingru; Chen, Zhixin; Guo, Zaiping; Zhang, Tao; Zhu, Shenmin; Zhang, Di

2015-06-03

A carbon/SnO2 composite (C-SnO2) with hierarchical photonic structure was fabricated from the templates of butterfly wings. We have investigated for the first time its application as the anode material for lithium-ion batteries. It was demonstrated to have high reversible capacities, good cycling stability, and excellent high-rate discharge performance, as shown by a capacitance of ∼572 mAh g(-1) after 100 cycles, 4.18 times that of commercial SnO2 powder (137 mAh g(-1)); a far better recovery capability of 94.3% was observed after a step-increase and sudden-recovery current. An obvious synergistic effect was found between the porous, hierarchically photonic microstructure and the presence of carbon; the synergy guarantees an effective flow of electrolyte and a short diffusion length of lithium ions, provides considerable buffering room, and prevents aggregation of SnO2 particles in the discharge/charge processes. This nature-inspired strategy points out a new direction for the fabrication of alternative anode materials.

Growth Mechanism of a Unique Hierarchical Vaterite Structure

NASA Astrophysics Data System (ADS)

Ma, Guobin; Xu, Yifei; Wang, Mu

2013-03-01

Calcium carbonate is one of the most significant minerals in nature as well as in biogenic sources. Calcium carbonate occurs naturally in three crystalline polymorphs, i.e., calcite, aragonite, and vaterite. Although it has been attracted much research attention to understanding of the formation mechanisms of the material, the properties of the vaterite polymorph is not well known. Here we report synthesis and formation mechanism of a unique hierarchical structure of vaterite. The material is grown by a controlled diffusion method. The structure possesses a core and an outer part. The core is convex lens-like and is formed by vaterite nanocrystals that have small misorientations. The outer part is separated into six garlic clove-like segments. Each segment possesses piles of plate-like vaterite crystals, and the orientations of the plates continuously change from pile to pile. Based on real-time experimental results and the structural analysis, a growth mechanism is presented. Work supported by NSFC (Grant No. 51172104) and MOST of China (Grant No. 2101CB630705)

Bioinspired Nanoscale Materials for Biomedical and Energy Applications

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

Bhattacharya, Priyanka; Du, Dan; Lin, Yuehe

2014-05-01

The demand of green, affordable and environmentally sustainable materials has encouraged scientists in different fields to draw inspiration from nature in developing materials with unique properties such as miniaturization, hierarchical organization, and adaptability. Together with the exceptional properties of nanomaterials, over the past century, the field of bioinspired nanomaterials has taken huge leaps. While on one hand, the sophistication of hierarchical structures endow biological systems with multifunctionality, the synthetic control on the creation of nanomaterials enables the design of materials with specific functionalities. The aim of this review is to provide a comprehensive, up-to-date overview of the field of bioinspiredmore » nanomaterials, which we have broadly categorized into biotemplates and biomimics. We will discuss the application of bioinspired nanomaterials as biotemplates in catalysis, nanomedicine, immunoassays and in energy, drawing attention to novel materials such as protein cages. Further, the applications of bioinspired materials in tissue engineering and biomineralization will also be discussed.« less

A hierarchical architecture S/MWCNT nanomicrosphere with large pores for lithium sulfur batteries.

PubMed

Chen, Jia-jia; Zhang, Qian; Shi, Yi-ning; Qin, Lin-lin; Cao, Yong; Zheng, Ming-sen; Dong, Quan-feng

2012-04-28

A hierarchical S/MWCNT nanomicrosphere for lithium/sulfur batteries with a high power and energy density as well as an excellent cycle life is introduced. Sulfur was uniformly coated on the surface of functional MWCNTs, which serves as a carbon matrix, to form a typical nanoscale core-shell structure with a sulfur layer of thickness 10-20 nm. Then the nanoscale sulfur intermediate composite was ball-milled to form interwoven and porous sphere architecture with large pores (around 1 μm to 5 μm). Different from most sulfur/carbon materials with micropore and mesopore structure, the micrometre scale S/MWCNT nanomicrosphere with a large pore structure could also exhibit high sulfur utilization and cycle retention. It could maintain a reversible capacity of 1000 mA h g(-1) after 100 cycles at 0.3 A g(-1) current density. And it even remained 780 mA h g(-1) after 200 cycles at 0.5 A g(-1) and 650 mA h g(-1) after 200 cycles at 1 A g(-1), showing a significant cyclability enhancement. It is believed that under the collective effect of hierarchical architecture, as well as the existence of carboxyl functional groups, sulfur/carbon materials with large pores could also exhibit an excellent electrochemical performance. The synthesis process introduced here is simple and broadly applicable, which would not only be beneficial to design new materials for lithium sulfur batteries but can also be extended to many different electrode materials for lithium ion batteries. This journal is © the Owner Societies 2012

Structural analysis of hierarchically organized zeolites

PubMed Central

Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Kärger, Jörg; Pérez-Ramírez, Javier

2015-01-01

Advances in materials synthesis bring about many opportunities for technological applications, but are often accompanied by unprecedented complexity. This is clearly illustrated by the case of hierarchically organized zeolite catalysts, a class of crystalline microporous solids that has been revolutionized by the engineering of multilevel pore architectures, which combine unique chemical functionality with efficient molecular transport. Three key attributes, the crystal, the pore and the active site structure, can be expected to dominate the design process. This review examines the adequacy of the palette of techniques applied to characterize these distinguishing features and their catalytic impact. PMID:26482337

A low-cost hierarchical nanostructured beta-titanium alloy with high strength

DOE PAGES

Devaraj, Arun; Joshi, Vineet V.; Srivastava, Ankit; ...

2016-04-01

Lightweighting of automobiles by use of novel low-cost, high strength-to-weight ratio structural materials can reduce the consumption of fossil fuels and in turn CO 2 emission. Working towards this goal we achieved high strength in a low cost β-titanium alloy, Ti-1Al-8V-5Fe (Ti185), by hierarchical nanostructure consisting of homogenous distribution of micron-scale and nanoscale α-phase precipitates within the β-phase matrix. The sequence of phase transformation leading to this hierarchical nanostructure is explored using electron microscopy and atom probe tomography. Our results suggest that the high number density of nanoscale α-phase precipitates in the β-phase matrix is due to ω assisted nucleationmore » of α resulting in high tensile strength, greater than any current commercial titanium alloy. Furthermore hierarchical nanostructured Ti185 serves as an excellent candidate for replacing costlier titanium alloys and other structural alloys for cost-effective lightweighting applications.« less

A low-cost hierarchical nanostructured beta-titanium alloy with high strength

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

Devaraj, Arun; Joshi, Vineet V.; Srivastava, Ankit

Lightweighting of automobiles by use of novel low-cost, high strength-to-weight ratio structural materials can reduce the consumption of fossil fuels and in turn CO 2 emission. Working towards this goal we achieved high strength in a low cost β-titanium alloy, Ti-1Al-8V-5Fe (Ti185), by hierarchical nanostructure consisting of homogenous distribution of micron-scale and nanoscale α-phase precipitates within the β-phase matrix. The sequence of phase transformation leading to this hierarchical nanostructure is explored using electron microscopy and atom probe tomography. Our results suggest that the high number density of nanoscale α-phase precipitates in the β-phase matrix is due to ω assisted nucleationmore » of α resulting in high tensile strength, greater than any current commercial titanium alloy. Furthermore hierarchical nanostructured Ti185 serves as an excellent candidate for replacing costlier titanium alloys and other structural alloys for cost-effective lightweighting applications.« less

Natural sisal fibers derived hierarchical porous activated carbon as capacitive material in lithium ion capacitor

NASA Astrophysics Data System (ADS)

Yang, Zhewei; Guo, Huajun; Li, Xinhai; Wang, Zhixing; Yan, Zhiliang; Wang, Yansen

2016-10-01

Lithium-ion capacitor (LIC) is a novel advanced electrochemical energy storage (EES) system bridging gap between lithium ion battery (LIB) and electrochemical capacitor (ECC). In this work, we report that sisal fiber activated carbon (SFAC) was synthesized by hydrothermal treatment followed by KOH activation and served as capacitive material in LIC for the first time. Different particle structure, morphology, specific surface area and heteroatoms affected the electrochemical performance of as-prepared materials and corresponding LICs. When the mass ratio of KOH to char precursor was 2, hierarchical porous structured SFAC-2 was prepared and exhibited moderate specific capacitance (103 F g-1 at 0.1 A g-1), superior rate capability and cyclic stability (88% capacity retention after 5000 cycles at 1 A g-1). The corresponding assembled LIC (LIC-SC2) with optimal comprehensive electrochemical performance, displayed the energy density of 83 Wh kg-1, the power density of 5718 W kg-1 and superior cyclic stability (92% energy density retention after 1000 cycles at 0.5 A g-1). It is worthwhile that the source for activated carbon is a natural and renewable one and the synthesis method is eco-friendly, which facilitate that hierarchical porous activated carbon has potential applications in the field of LIC and other energy storage systems.

Porous Carbon with Willow-Leaf-Shaped Pores for High-Performance Supercapacitors.

PubMed

Shi, Yanhong; Zhang, Linlin; Schon, Tyler B; Li, Huanhuan; Fan, Chaoying; Li, Xiaoying; Wang, Haifeng; Wu, Xinglong; Xie, Haiming; Sun, Haizhu; Seferos, Dwight S; Zhang, Jingping

2017-12-13

A novel kind of biomass-derived, high-oxygen-containing carbon material doped with nitrogen that has willow-leaf-shaped pores was synthesized. The obtained carbon material has an exotic hierarchical pore structure composed of bowl-shaped macropores, willow-leaf-shaped pores, and an abundance of micropores. This unique hierarchical porous structure provides an effective combination of high current densities and high capacitance because of a pseudocapacitive component that is afforded by the introduction of nitrogen and oxygen dopants. Our synthetic optimization allows further improvements in the performance of this hierarchical porous carbon (HPC) material by providing a high degree of control over the graphitization degree, specific surface area, and pore volume. As a result, a large specific surface area (1093 m 2 g -1 ) and pore volume (0.8379 cm 3 g -1 ) are obtained for HPC-650, which affords fast ion transport because of its short ion-diffusion pathways. HPC-650 exhibits a high specific capacitance of 312 F g -1 at 1 A g -1 , retaining 76.5% of its capacitance at 20 A g -1 . Moreover, it delivers an energy density of 50.2 W h kg -1 at a power density of 1.19 kW kg -1 , which is sufficient to power a yellow-light-emitting diode and operate a commercial scientific calculator.

Continuous flow chemical vapour deposition of carbon nanotube sea urchins.

PubMed

de La Verpilliere, Jean; Jessl, Sarah; Saeed, Khuzaimah; Ducati, Caterina; De Volder, Michael; Boies, Adam

2018-04-26

Hybrid structures consisting of functional materials enhanced by carbon nanotubes (CNTs) have potential for a variety of high impact applications, as shown by the impressive progress in sensing and mechanical applications enabled by CNT-enhanced materials. The hierarchical organisation of CNTs with other materials is key to the design of macroscale devices benefiting from the unique properties of individual CNTs, provided CNT density, morphology and binding with other materials are optimized. In this paper, we provide an analysis of a continuous aerosol process to create a hybrid hierarchical sea urchin structure with CNTs organized around a functional metal oxide core. We propose a new mechanism for the growth of these carbon nanotube sea urchins (CNTSU) and give new insight into their chemical composition. To corroborate the new mechanism, we examine the influence of CNT growth conditions on CNTSU morphology and demonstrate a new in-line characterisation technique to continuously monitor aerosol CNT growth during synthesis, which enables industrial-scale production optimization. Based upon the new formation mechanism we describe the first substrate-based chemical vapour deposition growth of CNTSUs which increases CNT length and improves G to D ratio, which also allows for the formation of CNTSU carpets with unique structures.

Hierarchical hollow spheres of Fe2O3 @polyaniline for lithium ion battery anodes.

PubMed

Jeong, Jae-Min; Choi, Bong Gill; Lee, Soon Chang; Lee, Kyoung G; Chang, Sung-Jin; Han, Young-Kyu; Lee, Young Boo; Lee, Hyun Uk; Kwon, Soonjo; Lee, Gaehang; Lee, Chang-Soo; Huh, Yun Suk

2013-11-20

Hierarchical hollow spheres of Fe2 O3 @polyaniline are fabricated by template-free synthesis of iron oxides followed by a post in- and exterior construction. A combination of large surface area with porous structure, fast ion/electron transport, and mechanical integrity renders this material attractive as a lithium-ion anode, showing superior rate capability and cycling performance. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template-free synthesis of nitrogen-doped hierarchical porous carbons for CO2 adsorption and supercapacitor electrodes.

PubMed

Bing, Xuefeng; Wei, Yanju; Wang, Mei; Xu, Sheng; Long, Donghui; Wang, Jitong; Qiao, Wenming; Ling, Licheng

2017-02-15

Nitrogen-doped hierarchical porous carbons (NHPCs) with controllable nitrogen content were prepared via a template-free method by direct carbonization of melamine-resorcinol-terephthaldehyde networks. The synthetic approach is facile and gentle, resulting in a hierarchical pore structure with modest micropores and well-developed meso-/macropores, and allowing the easy adjusting of the nitrogen content in the carbon framework. The micropore structure was generated within the highly cross-linked networks of polymer chains, while the mesopore and macropore structure were formed from the interconnected 3D gel network. The as-prepared NHPC has a large specific surface area of 1150m 2 ·g -1 , and a high nitrogen content of 14.5wt.%. CO 2 adsorption performances were measured between 0°C and 75°C, and a high adsorption capacity of 3.96mmol·g -1 was achieved at 1bar and 0°C. Moreover, these nitrogen-doped hierarchical porous carbons exhibit a great potential to act as electrode materials for supercapacitors, which could deliver high specific capacitance of 214.0F·g -1 with an excellent rate capability of 74.7% from 0.1 to 10 A·g -1 . The appropriate nitrogen doping and well-developed hierarchical porosity could accelerate the ion diffusion and the frequency response for excellent capacitive performance. This kind of new nitrogen-doped hierarchical porous carbons with controllable hierarchical porosity and chemical composition may have a good potential in the future applications. Copyright © 2016 Elsevier Inc. All rights reserved.

CryoTEM as an Advanced Analytical Tool for Materials Chemists.

PubMed

Patterson, Joseph P; Xu, Yifei; Moradi, Mohammad-Amin; Sommerdijk, Nico A J M; Friedrich, Heiner

2017-07-18

Morphology plays an essential role in chemistry through the segregation of atoms and/or molecules into different phases, delineated by interfaces. This is a general process in materials synthesis and exploited in many fields including colloid chemistry, heterogeneous catalysis, and functional molecular systems. To rationally design complex materials, we must understand and control morphology evolution. Toward this goal, we utilize cryogenic transmission electron microscopy (cryoTEM), which can track the structural evolution of materials in solution with nanometer spatial resolution and a temporal resolution of <1 s. In this Account, we review examples of our own research where direct observations by cryoTEM have been essential to understanding morphology evolution in macromolecular self-assembly, inorganic nucleation and growth, and the cooperative evolution of hybrid materials. These three different research areas are at the heart of our approach to materials chemistry where we take inspiration from the myriad examples of complex materials in Nature. Biological materials are formed using a limited number of chemical components and under ambient conditions, and their formation pathways were refined during biological evolution by enormous trial and error approaches to self-organization and biomineralization. By combining the information on what is possible in nature and by focusing on a limited number of chemical components, we aim to provide an essential insight into the role of structure evolution in materials synthesis. Bone, for example, is a hierarchical and hybrid material which is lightweight, yet strong and hard. It is formed by the hierarchical self-assembly of collagen into a macromolecular template with nano- and microscale structure. This template then directs the nucleation and growth of oriented, nanoscale calcium phosphate crystals to form the composite material. Fundamental insight into controlling these structuring processes will eventually allow us to design such complex materials with predetermined and potentially unique properties.

Mechanically enhanced nested-network hydrogels as a coating material for biomedical devices.

PubMed

Wang, Zhengmu; Zhang, Hongbin; Chu, Axel J; Jackson, John; Lin, Karen; Lim, Chinten James; Lange, Dirk; Chiao, Mu

2018-04-01

Well-organized composite formations such as hierarchical nested-network (NN) structure in bone tissue and reticular connective tissue present remarkable mechanical strength and play a crucial role in achieving physical and biological functions for living organisms. Inspired by these delicate microstructures in nature, an analogous scaffold of double network hydrogel was fabricated by creating a poly(2-hydroxyethyl methacrylate) (pHEMA) network in the porous structure of alginate hydrogels. The resulting hydrogel possessed hierarchical NN structure and showed significantly improved mechanical strength but still maintained high elasticity comparable to soft tissues due to a mutual strengthening effect between the two networks. The tough hydrogel is also self-lubricated, exhibiting a surface friction coefficient comparable with polydimethylsiloxane (PDMS) substrates lubricated by a commercial aqueous lubricant (K-Y Jelly) and other low surface friction hydrogels. Additional properties of this hydrogel include high hydrophilicity, good biocompatibility, tunable cell adhesion and bacterial resistance after incorporation of silver nanoparticles. Firm bonding of the hydrogel on silicone substrates could be achieved through facile chemical modification, thus enabling the use of this hydrogel as a versatile coating material for biomedical applications. In this study, we developed a tough hydrogel by crosslinking HEMA monomers in alginate hydrogels and forming a well-organized structure of hierarchical nested network (NN). Different from most reported stretchable alginate-based hydrogels, the NN hydrogel shows higher compressive strength but retains comparable softness to alginate counterparts. This work further demonstrated the good integration of the tough hydrogel with silicone substrates through chemical modification and micropillar structures. Other properties including surface friction, biocompatibility and bacterial resistance were investigated and the hydrogel shows a great promise as a versatile coating material for biomedical applications. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity.

PubMed

Schwieger, Wilhelm; Machoke, Albert Gonche; Weissenberger, Tobias; Inayat, Amer; Selvam, Thangaraj; Klumpp, Michael; Inayat, Alexandra

2016-06-13

'Hierarchy' is a property which can be attributed to a manifold of different immaterial systems, such as ideas, items and organisations or material ones like biological systems within living organisms or artificial, man-made constructions. The property 'hierarchy' is mainly characterised by a certain ordering of individual elements relative to each other, often in combination with a certain degree of branching. Especially mass-flow related systems in the natural environment feature special hierarchically branched patterns. This review is a survey into the world of hierarchical systems with special focus on hierarchically porous zeolite materials. A classification of hierarchical porosity is proposed based on the flow distribution pattern within the respective pore systems. In addition, this review might serve as a toolbox providing several synthetic and post-synthetic strategies to prepare zeolitic or zeolite containing material with tailored hierarchical porosity. Very often, such strategies with their underlying principles were developed for improving the performance of the final materials in different technical applications like adsorptive or catalytic processes. In the present review, besides on the hierarchically porous all-zeolite material, special focus is laid on the preparation of zeolitic composite materials with hierarchical porosity capable to face the demands of industrial application.

Recombination reduction on lead halide perovskite solar cells based on low temperature synthesized hierarchical TiO₂ nanorods.

PubMed

Jaramillo-Quintero, Oscar A; Solís de la Fuente, Mauricio; Sanchez, Rafael S; Recalde, Ileana B; Juarez-Perez, Emilio J; Rincón, Marina E; Mora-Seró, Iván

2016-03-28

Intensive research on the electron transport material (ETM) has been pursued to improve the efficiency of perovskite solar cells (PSCs) and decrease their cost. More importantly, the role of the ETM layer is not yet fully understood, and research on new device architectures is still needed. Here, we report the use of three-dimensional (3D) TiO2 with a hierarchical architecture based on rutile nanorods (NR) as photoanode material for PSCs. The proposed hierarchical nanorod (HNR) films were synthesized by a two-step low temperature (180 °C) hydrothermal method, and consist of TiO2 nanorod trunks with optimal lengths of 540 nm and TiO2 nanobranches with lengths of 45 nm. Different device configurations were fabricated with TiO2 structures (compact layer, NR and HNR) and CH3NH3PbI3, using different synthetic routes, as the active material. PSCs based on HNR-CH3NH3PbI3 achieved the highest power conversion efficiency compared to PSCs with other TiO2 structures. This result can be ascribed mainly to lower charge recombination as determined by impedance spectroscopy. Furthermore, we have observed that the CH3NH3PbI3 perovskite deposited by the two-step route shows higher efficiency, surface coverage and infiltration within the structure of 3D HNR than the one-step CH3NH3PbI(3-x)Cl(x) perovskite.

Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

PubMed

Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

2015-12-09

Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

Facile synthesis of a two-tier hierarchical structured superhydrophobic-superoleophilic melamine sponge for rapid and efficient oil/water separation.

PubMed

Chen, Jiucun; You, Hui; Xu, Liqun; Li, Tianhao; Jiang, Xianquan; Li, Chang Ming

2017-11-15

Oil leakages often cause fatal disasters for environmental pollution but an efficient treatment of the oil spills is still very challenging. Sponge-substrates with superhydrophobicity and superoleophilicity have been attracted much attention for oil/water separation. In this study, an inexpensive commercial melamine sponge was chemically modified for the uses of oil spills treatment by oil/water separation. Inspiring from the superhydrophobic property of lotus leaf, pyrrole was polymerized by a simple vapor-phase deposition to encapsulate the raw melamine-formaldehyde (MF) sponge. The as-formed thin polypyrrole walls were utilized as reducing reagent to generate Ag nanoparticles on the capsuled sponge. Accordingly, a superhydrophobic melamine sponge with a two-tier hierarchical structure was achieved after fluorination, and this material was applied to absorb oil from water. The absorption capacity, absorption rate and recyclability were investigated. This superhydrophobic sponge exhibited an efficient and fast oil/water separation performance in complicated environment and could be applied in industrial production because of its low cost and simple fabrication procedure. This study presents a facile strategy for the fabrication of efficient oil sorbents based on a two-tier hierarchical structure, providing a novel means for the upgrading of engineered sorption materials. Copyright © 2017 Elsevier Inc. All rights reserved.

Passive and active mechanical properties of biotemplated ceramics revisited.

PubMed

Van Opdenbosch, Daniel; Fritz-Popovski, Gerhard; Plank, Johann; Zollfrank, Cordt; Paris, Oskar

2016-10-13

Living nature and human technology apply different principles to create hard, strong and tough materials. In this review, we compare and discuss prominent aspects of these alternative strategies, and demonstrate for selected examples that nanoscale-precision biotemplating is able to produce uncommon mechanical properties as well as actuating behavior, resembling to some extent the properties of the original natural templates. We present and discuss mechanical testing data showing for the first time that nanometer-precision biotemplating can lead to porous ceramic materials with deformation characteristics commonly associated with either biological or highly advanced technical materials. We also review recent findings on the relation between hierarchical structuring and humidity-induced directional motion. Finally, we discuss to which extent the observed behavior is in agreement with previous results and theories on the mechanical properties of multiscale hierarchical materials, as well as studies of highly disperse technical materials, together with an outlook for further lines of investigation.

Hierarchical LiMn2O4 Hollow Cubes with Exposed {111} Planes as High-Power Cathodes for Lithium-Ion Batteries.

PubMed

Wu, Yu; Cao, Chuanbao; Zhang, Junting; Wang, Lin; Ma, Xilan; Xu, Xingyan

2016-08-03

Hierarchical LiMn2O4 hollow cubes with exposed {111} planes have been synthesized using cube-shaped MnCO3 precursors, which are fabricated through a facile co-precipitation reaction. Without surface modification, the as-prepared LiMn2O4 exhibits excellent cyclability and superior rate capability. Surprisingly, even over 70% of primal discharge capacity can be maintained for up to 1000 cycles at 50 C, and with only about 72 s of discharge time the as-prepared materials can deliver initial discharge capacity of 96.5 mA h g(-1). What is more, the materials have 98.4% and 90.7% capacity retentions for up to 100 cycles at 5 C under the temperatures of 25 and 60 °C, respectively. The superior electrochemical performance can be attributed to the unique hierarchical and interior hollow structure, exposed {111} planes, and high-quality crystallinity.

Hierarchical TiO2/C nanocomposite monoliths with a robust scaffolding architecture, mesopore-macropore network and TiO2-C heterostructure for high-performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Hai-Bo; Yang, Yue; Chen, Li-Hua; Wang, Yun; Huang, Shao-Zhuan; Tao, Jia-Wei; Ma, Xiao-Ting; Hasan, Tawfique; Li, Yu; Xu, Yan; Su, Bao-Lian

2016-05-01

Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500, obtained by calcination at 500 °C in nitrogen, contains an anatase TiO2-C heterostructure with a specific surface area of 66.5 m2 g-1. When evaluated as an anode material at 0.5 C, TiO2/C-500 exhibits a high and reversible lithium storage capacity of 188 mA h g-1, an excellent initial capacity of 283 mA h g-1, a long cycle life with a 94% coulombic efficiency preserved after 200 cycles, and a very low charge transfer resistance. The superior electrochemical performance of TiO2/C-500 is attributed to the synergistic effect of high electrical conductivity, anatase TiO2-C heterostructure, mesopore-macropore network and robust scaffolding architecture. The current material strategy affords a general approach for the design of complex inorganic nanocomposites with structural stability, and tunable and interconnected hierarchical porosity that may lead to the next generation of electrochemical supercapacitors with high energy efficiency and superior power density.Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500, obtained by calcination at 500 °C in nitrogen, contains an anatase TiO2-C heterostructure with a specific surface area of 66.5 m2 g-1. When evaluated as an anode material at 0.5 C, TiO2/C-500 exhibits a high and reversible lithium storage capacity of 188 mA h g-1, an excellent initial capacity of 283 mA h g-1, a long cycle life with a 94% coulombic efficiency preserved after 200 cycles, and a very low charge transfer resistance. The superior electrochemical performance of TiO2/C-500 is attributed to the synergistic effect of high electrical conductivity, anatase TiO2-C heterostructure, mesopore-macropore network and robust scaffolding architecture. The current material strategy affords a general approach for the design of complex inorganic nanocomposites with structural stability, and tunable and interconnected hierarchical porosity that may lead to the next generation of electrochemical supercapacitors with high energy efficiency and superior power density. Electronic supplementary information (ESI) available: Characterizing BC aerogel; TG/DTA curves of BC@TiO2; EDX spectrum of TiO2/C-500; photograph of BC@TiO2 and TiO2/C-500 monoliths; XRD patterns of TiO2/C-T monoliths under a nitrogen atmosphere; characterizing TiO2/C-T and TiO2-500; XPS of TiO2/C-500; cycling performance of TiO2/C-T; capacity retention plots, coulombic efficiency, EIS spectra after 10 cycles and the initial EIS spectra of TiO2/C-500; XRD patterns of TiO2/C-500 before and after 150 discharge-charge cycles at 0.5 C. See DOI: 10.1039/c5nr09149g

Hierarchically-driven Approach for Quantifying Materials Uncertainty in Creep Deformation and Failure of Aerospace Materials

DTIC Science & Technology

2016-07-01

characteristics and to examine the sensitivity of using such techniques for evaluating microstructure. In addition to the GUI tool, a manual describing its use has... Evaluating Local Primary Dendrite Arm Spacing Characterization Techniques Using Synthetic Directionally Solidified Dendritic Microstructures, Metallurgical and...driven approach for quanti - fying materials uncertainty in creep deformation and failure of aerspace materials, Multi-scale Structural Mechanics and

Oxygen-rich hierarchical porous carbon made from pomelo peel fiber as electrode material for supercapacitor

NASA Astrophysics Data System (ADS)

Li, Jing; Liu, Wenlong; Xiao, Dan; Wang, Xinhui

2017-09-01

Oxygen-rich hierarchical porous carbon has been fabricated using pomelo peel fiber as a carbon source via an improved KOH activation method. The morphology and chemical composition of the obtained carbon materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), electron microscopy (EM), Raman spectra and elemental analysis. The unique porous structure with abundant oxygen functional groups is favorable to capacitive behavior, and the as-prepared carbon material exhibits high specific capacitance of 222.6 F g-1 at 0.5 A g-1 in 6 M KOH and superior stability over 5000 cycles. This work not only describes a simple way to prepare high-performance carbon material from the discarded pomelo peel, but also provides a strategy for its disposal issue and contributes to the environmental improvement.

Spinous α-Fe2O3 hierarchical structures anchored on Ni foam for supercapacitor electrodes and visible light driven photocatalysts.

PubMed

Zheng, Xin; Han, Zhicheng; Yao, Shunyu; Xiao, Huanhao; Chai, Fang; Qu, Fengyu; Wu, Xiang

2016-04-28

Spinous α-Fe2O3 hierarchical structures grown on a Ni foam substrate have been successfully obtained by a facile one-step hydrothermal method. The prepared products are functionalized as supercapacitor electrodes without adding any ancillary materials such as carbon black or binders. Their electrochemical properties show a high discharge areal capacitance (681 mF cm(-2) at 1 mA cm(-2)), good rate performance (495 mF cm(-2) at 5 mA cm(-2)) and long-term cycling stability (23.9% loss after 6000 repetitive cycles at 1 mA cm(-2)). Such excellent supercapacitive characteristics could be mainly attributed to their unique spatial structures which provide many active sites and enhance the combination between the electrode and Ni foam to support fast ion and electron transfer. In addition, the prepared α-Fe2O3 product is also used as a photocatalyst for the photocatalytic degradation of several harmful organic dyes under visible light illumination. By comparing the photocatalytic performance towards Congo red dye with other photocatalysts, it was observed that the prepared spinous α-Fe2O3 hierarchical structure exhibited superior photocatalytic performance. Finally, photocatalytic recycle tests showed the superiority of the prepared α-Fe2O3 product. This demonstrates that spinous α-Fe2O3 structures could be promising candidate materials for high-capacity, low-cost supercapacitor electrodes and environmentally friendly photocatalysts.

Water decontamination by polyoxometalate-functionalized 3D-printed hierarchical porous devices.

PubMed

Ji, Yuanchun; Ma, Yuan; Ma, Yanjiao; Asenbauer, Jakob; Passerini, Stefano; Streb, Carsten

2018-03-25

The design of organic-inorganic hybrid composites has revolutionized application-driven materials design. Here, we show how hierarchically structured, 3D-printed ABS polymers can be surface-functionalized with lacunary polyoxometalate anions ([α-PW 9 O 34 ] 9- ) featuring heavy-metal binding sites. The resulting composite is highly porous and can be used for the removal of transition-metal pollutants from water. Thus, a facile blueprint for decentralized production of water filtration devices is reported.

Bioinspired fabrication of hierarchically structured, pH-tunable photonic crystals with unique transition.

PubMed

Yang, Qingqing; Zhu, Shenmin; Peng, Wenhong; Yin, Chao; Wang, Wanlin; Gu, Jiajun; Zhang, Wang; Ma, Jun; Deng, Tao; Feng, Chuanliang; Zhang, Di

2013-06-25

We herein report a new class of photonic crystals with hierarchical structures, which are of color tunability over pH. The materials were fabricated through the deposition of polymethylacrylic acid (PMAA) onto a Morpho butterfly wing template by using a surface bonding and polymerization route. The amine groups of chitosan in Morpho butterfly wings provide reaction sites for the MAA monomer, resulting in hydrogen bonding between the template and MAA. Subsequent polymerization results in PMAA layers coating homogenously on the hierarchical photonic structures of the biotemplate. The pH-induced color change was detected by reflectance spectra as well as optical observation. A distinct U transition with pH was observed, demonstrating PMAA content-dependent properties. The appearance of the unique U transition results from electrostatic interaction between the -NH3(+) of chitosan and the -COO(-) groups of PMAA formed, leading to a special blue-shifted point at the pH value of the U transition, and the ionization of the two functional groups in the alkali and acid environment separately, resulting in a red shift. This work sets up a strategy for the design and fabrication of tunable photonic crystals with hierarchical structures, which provides a route for combining functional polymers with biotemplates for wide potential use in many fields.

A Feasible One-Step Synthesis of Hierarchical Zeolite Beta with Uniform Nanocrystals via CTAB

PubMed Central

Zhang, Weimin; Hu, Sufang; Qin, Bo; Li, Ruifeng

2018-01-01

A hierarchical zeolite Beta has been prepared by a feasible one-pot and one-step method, which is suitable for application in industrial production. The synthesis is a simple hydrothermal process with low-cost raw materials, without adding alcohol or adding seeds, and without aging, recrystallization, and other complex steps. The hierarchical zeolite Beta is a uniform nanocrystal (20–50 nm) aggregation with high external surface area (300 m2/g) and mesoporous volume (0.50 cm3/g), with the mesoporous structure composed of intercrystal and intracrystal pores. As an acid catalyst in benzylation of naphthalene with benzyl chloride, the hierarchical zeolite Beta has shown high activity in the bulky molecule reaction due to its introduction of mesostructure. PMID:29695044

A three-dimensional hierarchical collagen scaffold fabricated by a combined solid freeform fabrication (SFF) and electrospinning process to enhance mesenchymal stem cell (MSC) proliferation

NASA Astrophysics Data System (ADS)

Ahn, SeungHyun; Koh, Young Ho; Kim, GeunHyung

2010-06-01

Collagen has the advantage of being very similar to macromolecular substances that can be recognized and metabolized in the biological environment. Although the natural material has superior property for this purpose, its use to fabricate reproducible and pore-structure-controlled 3D structures, which are designed to allow the entry of sufficient cells and the easy diffusion of nutrients, has been limited due to its low processability. Here, we propose a hybrid technology that combines a cryogenic plotting system with an electrospinning process. Using this technique, an easily pore-size-controllable hierarchical 3D scaffold consisting of micro-sized highly porous collagen strands and micro/nano-sized collagen fibers was fabricated. The pore structure of the collagen scaffold was controlled by the collagen micro/nanofibers, which were layered in the scaffold. The hierarchical scaffolds were characterized with respect to initial cell attachment and proliferation of bone marrow-derived mesenchymal stem cells within the scaffolds. The hierarchical scaffold exhibited incredibly enhanced initial cell attachment and cell compactness between pores of the plotted scaffold relative to the normally designed 3D collagen scaffold.

High-rate and long-life lithium-ion battery performance of hierarchically hollow-structured NiCo 2O 4/CNT nanocomposite

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

Wang, Jie; Wu, Jianzhong; Wu, Zexing

In this paper, 3D-transition binary metal oxides have been considered as promising anode materials for lithium-ion batteries with improved reversible capacity, structural stability and electronic conductivity compared with single metal oxides. Here, carbon nanotube supported NiCo 2O 4 nanoparticles (NiCo 2O 4/CNT) with 3D hierarchical hollow structure are fabricated via a simple one-pot method. The NiCo 2O 4 nanoparticles with interconnected pores are consists of small nanocrystals. When used as anode material for the lithium-ion battery, NiCo 2O 4/CNT exhibits enhanced electrochemical performance than that of Co 3O 4/CNT and NiO/CNT. Moreover, ultra-high discharge/charge stability was obtained for 4000 cyclesmore » at a current density of 5 A g –1. The superior battery performance of NiCo 2O 4 nanoparticles is probably attributed to the special structural features and physical characteristics, including integrity, hollow structure with interconnected pores, which providing sufficient accommodation for the volume change during charge/discharge process. Besides, the consisting of ultra-small crystals enhanced the utility of active material, and intimate interaction with CNTs improved the electron-transfer rate.« less

High-rate and long-life lithium-ion battery performance of hierarchically hollow-structured NiCo 2O 4/CNT nanocomposite

DOE PAGES

Wang, Jie; Wu, Jianzhong; Wu, Zexing; ...

2017-05-17

In this paper, 3D-transition binary metal oxides have been considered as promising anode materials for lithium-ion batteries with improved reversible capacity, structural stability and electronic conductivity compared with single metal oxides. Here, carbon nanotube supported NiCo 2O 4 nanoparticles (NiCo 2O 4/CNT) with 3D hierarchical hollow structure are fabricated via a simple one-pot method. The NiCo 2O 4 nanoparticles with interconnected pores are consists of small nanocrystals. When used as anode material for the lithium-ion battery, NiCo 2O 4/CNT exhibits enhanced electrochemical performance than that of Co 3O 4/CNT and NiO/CNT. Moreover, ultra-high discharge/charge stability was obtained for 4000 cyclesmore » at a current density of 5 A g –1. The superior battery performance of NiCo 2O 4 nanoparticles is probably attributed to the special structural features and physical characteristics, including integrity, hollow structure with interconnected pores, which providing sufficient accommodation for the volume change during charge/discharge process. Besides, the consisting of ultra-small crystals enhanced the utility of active material, and intimate interaction with CNTs improved the electron-transfer rate.« less

Bioinspired Design: Magnetic Freeze Casting

NASA Astrophysics Data System (ADS)

Porter, Michael Martin

Nature is the ultimate experimental scientist, having billions of years of evolution to design, test, and adapt a variety of multifunctional systems for a plethora of diverse applications. Next-generation materials that draw inspiration from the structure-property-function relationships of natural biological materials have led to many high-performance structural materials with hybrid, hierarchical architectures that fit form to function. In this dissertation, a novel materials processing method, magnetic freeze casting, is introduced to develop porous scaffolds and hybrid composites with micro-architectures that emulate bone, abalone nacre, and other hard biological materials. This method uses ice as a template to form ceramic-based materials with continuously, interconnected microstructures and magnetic fields to control the alignment of these structures in multiple directions. The resulting materials have anisotropic properties with enhanced mechanical performance that have potential applications as bone implants or lightweight structural composites, among others.

Three-Dimensional CdS/Au Butterfly Wing Scales with Hierarchical Rib Structures for Plasmon-Enhanced Photocatalytic Hydrogen Production.

PubMed

Fang, Jing; Gu, Jiajun; Liu, Qinglei; Zhang, Wang; Su, Huilan; Zhang, Di

2018-06-13

Localized surface plasmon resonance (LSPR) of plasmonic metals (e.g., Au) can help semiconductors improve their photocatalytic hydrogen (H 2 ) production performance. However, an artificial synthesis of hierarchical plasmonic structures down to nanoscales is usually difficult. Here, we adopt the butterfly wing scales from Morpho didius to fabricate three-dimensional (3D) CdS/Au butterfly wing scales for plasmonic photocatalysis. The as-prepared materials well-inherit the pristine hierarchical biostructures. The 3D CdS/Au butterfly wing scales exhibit a high H 2 production rate (221.8 μmol·h -1 within 420-780 nm), showing a 241-fold increase over the CdS butterfly wing scales. This is attributed to the effective potentiation effect of LSPR introduced by multilayer metallic rib structures and a good interface bonding state between Au and CdS nanoparticles. Thus, our study provides a relatively simple method to learn from nature and inspiration for preparing highly efficient plasmonic photocatalysts.

Organic materials as templates for the formation of mesoporous inorganic materials and ordered inorganic nanocomposites

NASA Astrophysics Data System (ADS)

Ziegler, Christopher R.

Hierarchically structured inorganic materials are everywhere in nature. From unicellular aquatic algae such as diatoms to the bones and/or cartilage that comprise the skeletal systems of vertebrates. Complex mechanisms involving site-specific chemistries and precision kinetics are responsible for the formation of such structures. In the synthetic realm, reproduction of even the most basic hierarchical structure effortlessly produced in nature is difficult. However, through the utilization of self-assembling structures or "templates", such as polymers or amphiphilic surfactants, combined with some favorable interaction between a chosen inorganic, the potential exists to imprint an inorganic material with a morphology dictated via synthetic molecular self-assembly. In doing so, a very basic hierarchical structure is formed on the angstrom and nanometer scales. The work presented herein utilizes the self-assembly of either surfactants or block copolymers with the desired inorganic or inorganic precursor to form templated inorganic structures. Specifically, mesoporous silica spheres and copolymer directed calcium phosphate-polymer composites were formed through the co-assembly of an organic template and a precursor to form the desired mesostructured inorganic. For the case of the mesoporous silica spheres, a silica precursor was mixed with cetyltrimethylammonium bromide and cysteamine, a highly effective biomimetic catalyst for the conversion of alkoxysilanes to silica. Through charge-based interactions between anionic silica species and the micelle-forming cationic surfactant, ordered silica structures resulted. The incorporation of a novel, effective catalyst was found to form highly condensed silica spheres for potential application as catalyst supports or an encapsulation media. Ordered calcium phosphate-polymer composites were formed using two routes. Both routes take advantage of hydrogen bonding and ionic interactions between the calcium and phosphate precursors and the self-assembling copolymer template. Some evidence suggests that the copolymer morphology remained in the composite despite the known tendency for calcium phosphates to form highly elongated crystalline structures with time, as is commonly the case for synthetic hydroxyapatites. Such materials have obvious application as bone grafts and bone coatings due, in part, to the osteoconductive nature of calcium phosphate as well as to the mesoporosity generated through the cooperative assembly of the block copolymer and the inorganic. Future work, including potential experiments to determine osteoconductivity of as-prepared composites, is also presented herein.

Multi-Scale Hierarchical and Topological Design of Structures for Failure Resistance

DTIC Science & Technology

2013-10-04

materials, simulation, 3D printing , advanced manufacturing, design, fracture Markus J. Buehler Massachusetts Institute of Technology (MIT) 77...by Mineralized Natural Materials: Computation, 3D printing , and Testing, Advanced Functional Materials, (09 2013): 0. doi: 10.1002/adfm.201300215 10...have made substantial progress. Recent work focuses on the analysis of topological effects of composite design, 3D printing of bioinspired and

High-performance asymmetric supercapacitors based on multilayer MnO2 /graphene oxide nanoflakes and hierarchical porous carbon with enhanced cycling stability.

PubMed

Zhao, Yufeng; Ran, Wei; He, Jing; Huang, Yizhong; Liu, Zhifeng; Liu, Wei; Tang, Yongfu; Zhang, Long; Gao, Dawei; Gao, Faming

2015-03-18

In this work, MnO(2)/GO (graphene oxide) composites with novel multilayer nanoflake structure, and a carbon material derived from Artemia cyst shell with genetic 3D hierarchical porous structure (HPC), are prepared. An asymmetric supercapacitor has been fabricated using MnO(2)/GO as positive electrode and HPC as negative electrode material. Because of their unique structures, both MnO(2)/GO composites and HPC exhibit excellent electrochemical performances. The optimized asymmetric supercapacitor could be cycled reversibly in the high voltage range of 0-2 V in aqueous electrolyte, which exhibits maximum energy density of 46.7 Wh kg(-1) at a power density of 100 W kg(-1) and remains 18.9 Wh kg(-1) at 2000 W kg(-1). Additionally, such device also shows superior long cycle life along with ∼100% capacitance retention after 1000 cycles and ∼93% after 4000 cycles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-contact tensile viscoelastic characterization of microscale biological materials

NASA Astrophysics Data System (ADS)

Li, Yuhui; Hong, Yuan; Xu, Guang-Kui; Liu, Shaobao; Shi, Qiang; Tang, Deding; Yang, Hui; Genin, Guy M.; Lu, Tian Jian; Xu, Feng

2018-06-01

Many structures and materials in nature and physiology have important "meso-scale" structures at the micron length-scale whose tensile responses have proven difficult to characterize mechanically. Although techniques such as atomic force microscopy and micro- and nano-identation are mature for compression and indentation testing at the nano-scale, and standard uniaxial and shear rheometry techniques exist for the macroscale, few techniques are applicable for tensile-testing at the micrometre-scale, leaving a gap in our understanding of hierarchical biomaterials. Here, we present a novel magnetic mechanical testing (MMT) system that enables viscoelastic tensile testing at this critical length scale. The MMT system applies non-contact loading, avoiding gripping and surface interaction effects. We demonstrate application of the MMT system to the first analyses of the pure tensile responses of several native and engineered tissue systems at the mesoscale, showing the broad potential of the system for exploring micro- and meso-scale analysis of structured and hierarchical biological systems.

Non-contact tensile viscoelastic characterization of microscale biological materials

NASA Astrophysics Data System (ADS)

Li, Yuhui; Hong, Yuan; Xu, Guang-Kui; Liu, Shaobao; Shi, Qiang; Tang, Deding; Yang, Hui; Genin, Guy M.; Lu, Tian Jian; Xu, Feng

2018-01-01

Many structures and materials in nature and physiology have important "meso-scale" structures at the micron length-scale whose tensile responses have proven difficult to characterize mechanically. Although techniques such as atomic force microscopy and micro- and nano-identation are mature for compression and indentation testing at the nano-scale, and standard uniaxial and shear rheometry techniques exist for the macroscale, few techniques are applicable for tensile-testing at the micrometre-scale, leaving a gap in our understanding of hierarchical biomaterials. Here, we present a novel magnetic mechanical testing (MMT) system that enables viscoelastic tensile testing at this critical length scale. The MMT system applies non-contact loading, avoiding gripping and surface interaction effects. We demonstrate application of the MMT system to the first analyses of the pure tensile responses of several native and engineered tissue systems at the mesoscale, showing the broad potential of the system for exploring micro- and meso-scale analysis of structured and hierarchical biological systems.

Emerging optical properties from the combination of simple optical effects

NASA Astrophysics Data System (ADS)

England, Grant T.; Aizenberg, Joanna

2018-01-01

Structural color arises from the patterning of geometric features or refractive indices of the constituent materials on the length-scale of visible light. Many different organisms have developed structurally colored materials as a means of creating multifunctional structures or displaying colors for which pigments are unavailable. By studying such organisms, scientists have developed artificial structurally colored materials that take advantage of the hierarchical geometries, frequently employed for structural coloration in nature. These geometries can be combined with absorbers—a strategy also found in many natural organisms—to reduce the effects of fabrication imperfections. Furthermore, artificial structures can incorporate materials that are not available to nature—in the form of plasmonic nanoparticles or metal layers—leading to a host of novel color effects. Here, we explore recent research involving the combination of different geometries and materials to enhance the structural color effect or to create entirely new effects, which cannot be observed otherwise.

Hierarchical regrowth of flowerlike nanographene sheets on oxygen-plasma-treated carbon nanowalls

NASA Astrophysics Data System (ADS)

Shimoeda, Hironao; Kondo, Hiroki; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

2014-04-01

Cauliflorous nanographene sheets were hierarchically regrown on the spearlike structures of carbon nanowalls (CNWs) produced by O2-plasma etching. The spears on the CNWs acted as a stem for the growth of flowerlike flaky nanographene sheets, where the root of the nanoflower was located at a defect or disordered site. The defects on the graphitic structures were induced by irradiation with oxygen-related radicals and ions in the O2-based plasmas and acted as sites for the nucleation of flowerlike nanographene. The porous carbon nanostructures regrown after O2-plasma treatment have a relatively higher surface area and are thus promising materials for electrochemical applications.

Fabrication of bristlegrass-like VO2 (B)-ZnO heteroarchitectures as anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ma, Yining; Li, Wenjing; Ji, Shidong; Zhou, Huaijuan; Li, Rong; Li, Ning; Yao, Heliang; Cao, Xun; Jin, Ping

2017-08-01

Three-dimensional bristlegrass-like hierarchical VO2 (B)-ZnO heteroarchitectures with ZnO nanorods grown radially on VO2 (B) nanorods were successfully fabricated via a simple two-step synthesized method. When applied as an anode material for lithium-ion batteries, the VO2 (B)-ZnO hybrid electrode exhibited high reversible capacity and excellent recyclability, which could be originated from the unique hierarchical structure of the bristlegrass. After 80 cycles, the nanocomposite still maintained a higher reversible capacity of 329.4 mA h g-1 at a current density of 50 mA g-1. Therefore, the particular architecture of VO2 (B)-ZnO nanocomposite can be a promising candidate as the anode material in lithium-ion batteries.

Smectic Layer Origami via Preprogrammed Photoalignment.

PubMed

Ma, Ling-Ling; Tang, Ming-Jie; Hu, Wei; Cui, Ze-Qun; Ge, Shi-Jun; Chen, Peng; Chen, Lu-Jian; Qian, Hao; Chi, Li-Feng; Lu, Yan-Qing

2017-04-01

Hierarchical architecture is of vital importance in soft materials. Focal conic domains (FCDs) of smectic liquid crystals, characterized by an ordered lamellar structure, attract intensive attention. Simultaneously tailoring the geometry and clustering characteristics of FCDs remains a challenge. Here, the 3D smectic layer origami via a 2D preprogrammed photoalignment film is accomplished. Full control of hierarchical superstructures is demonstrated, including the domain size, shape, and orientation, and the lattice symmetry of fragmented toric FCDs. The unique symmetry breaking of resultant superstructures combined with the optical anisotropy of the liquid crystals induces an intriguing polarization-dependent diffraction. This work broadens the scientific understanding of self-assembled soft materials and may inspire new opportunities for advanced functional materials and devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stretchable conducting materials with multi-scale hierarchical structures for biomedical applications

NASA Astrophysics Data System (ADS)

Kim, Hyun; Shim, Bong Sup

2014-08-01

Electrogenetic tissues in human body such as central and peripheral nerve systems, muscular and cardiomuscular systems are soft and stretchable materials. However, most of the artificial materials, interfacing with those conductive tissues, such as neural electrodes and cardiac pacemakers, have stiff mechanical properties. The rather contradictory properties between natural and artificial materials usually cause critical incompatibility problems in implanting bodymachine interfaces for wide ranges of biomedical devices. Thus, we developed a stretchable and electrically conductive material with complex hierarchical structures; multi-scale microstructures and nanostructural electrical pathways. For biomedical purposes, an implantable polycaprolactone (PCL) membrane was coated by molecularly controlled layer-bylayer (LBL) assembly of single-walled carbon nanotubes (SWNTs) or poly(3,4-ethylenedioxythiophene) (PEDOT). The soft PCL membrane with asymmetric micro- and nano-pores provides elastic properties, while conductive SWNT or PEDOT coating preserves stable electrical conductivity even in a fully stretched state. This electrical conductivity enhanced ionic cell transmission and cell-to-cell interactions as well as electrical cellular stimulation on the membrane. Our novel stretchable conducting materials will overcome long-lasting challenges for bioelectronic applications by significantly reducing mechanical property gaps between tissues and artificial materials and by providing 3D interconnected electro-active pathways which can be available even at a fully stretched state.

PdCo/Pd-Hexacyanocobaltate Hybrid Nanoflowers: Cyanogel-Bridged One-Pot Synthesis and Their Enhanced Catalytic Performance

NASA Astrophysics Data System (ADS)

Liu, Zhen-Yuan; Fu, Geng-Tao; Zhang, Lu; Yang, Xiao-Yu; Liu, Zhen-Qi; Sun, Dong-Mei; Xu, Lin; Tang, Ya-Wen

2016-08-01

Elaborate architectural manipulation of nanohybrids with multi-components into controllable 3D hierarchical structures is of great significance for both fundamental scientific interest and realization of various functionalities, yet remains a great challenge because different materials with distinct physical/chemical properties could hardly be incorporated simultaneously into the synthesis process. Here, we develop a novel one-pot cyanogel-bridged synthetic approach for the generation of 3D flower-like metal/Prussian blue analogue nanohybrids, namely PdCo/Pd-hexacyanocobaltate for the first time. The judicious introduction of polyethylene glycol (PEG) and the formation of cyanogel are prerequisite for the successful fabrication of such fascinating hierarchical nanostructures. Due to the unique 3D hierarchical structure and the synergistic effect between hybrid components, the as-prepared hybrid nanoflowers exhibit a remarkable catalytic activity and durability toward the reduction of Rhodamine B (RhB) by NaBH4. We expect that the obtained hybrid nanoflowers may hold great promises in water remediation field and beyond. Furthermore, the facile synthetic strategy presented here for synthesizing functional hybrid materials can be extendable for the synthesis of various functional hybrid nanomaterials owing to its versatility and feasibility.

PdCo/Pd-Hexacyanocobaltate Hybrid Nanoflowers: Cyanogel-Bridged One-Pot Synthesis and Their Enhanced Catalytic Performance.

PubMed

Liu, Zhen-Yuan; Fu, Geng-Tao; Zhang, Lu; Yang, Xiao-Yu; Liu, Zhen-Qi; Sun, Dong-Mei; Xu, Lin; Tang, Ya-Wen

2016-08-30

Elaborate architectural manipulation of nanohybrids with multi-components into controllable 3D hierarchical structures is of great significance for both fundamental scientific interest and realization of various functionalities, yet remains a great challenge because different materials with distinct physical/chemical properties could hardly be incorporated simultaneously into the synthesis process. Here, we develop a novel one-pot cyanogel-bridged synthetic approach for the generation of 3D flower-like metal/Prussian blue analogue nanohybrids, namely PdCo/Pd-hexacyanocobaltate for the first time. The judicious introduction of polyethylene glycol (PEG) and the formation of cyanogel are prerequisite for the successful fabrication of such fascinating hierarchical nanostructures. Due to the unique 3D hierarchical structure and the synergistic effect between hybrid components, the as-prepared hybrid nanoflowers exhibit a remarkable catalytic activity and durability toward the reduction of Rhodamine B (RhB) by NaBH4. We expect that the obtained hybrid nanoflowers may hold great promises in water remediation field and beyond. Furthermore, the facile synthetic strategy presented here for synthesizing functional hybrid materials can be extendable for the synthesis of various functional hybrid nanomaterials owing to its versatility and feasibility.

PdCo/Pd-Hexacyanocobaltate Hybrid Nanoflowers: Cyanogel-Bridged One-Pot Synthesis and Their Enhanced Catalytic Performance

PubMed Central

Liu, Zhen-Yuan; Fu, Geng-Tao; Zhang, Lu; Yang, Xiao-Yu; Liu, Zhen-Qi; Sun, Dong-Mei; Xu, Lin; Tang, Ya-Wen

2016-01-01

Elaborate architectural manipulation of nanohybrids with multi-components into controllable 3D hierarchical structures is of great significance for both fundamental scientific interest and realization of various functionalities, yet remains a great challenge because different materials with distinct physical/chemical properties could hardly be incorporated simultaneously into the synthesis process. Here, we develop a novel one-pot cyanogel-bridged synthetic approach for the generation of 3D flower-like metal/Prussian blue analogue nanohybrids, namely PdCo/Pd-hexacyanocobaltate for the first time. The judicious introduction of polyethylene glycol (PEG) and the formation of cyanogel are prerequisite for the successful fabrication of such fascinating hierarchical nanostructures. Due to the unique 3D hierarchical structure and the synergistic effect between hybrid components, the as-prepared hybrid nanoflowers exhibit a remarkable catalytic activity and durability toward the reduction of Rhodamine B (RhB) by NaBH4. We expect that the obtained hybrid nanoflowers may hold great promises in water remediation field and beyond. Furthermore, the facile synthetic strategy presented here for synthesizing functional hybrid materials can be extendable for the synthesis of various functional hybrid nanomaterials owing to its versatility and feasibility. PMID:27573057

Ferritic Alloys with Extreme Creep Resistance via Coherent Hierarchical Precipitates

PubMed Central

Song, Gian; Sun, Zhiqian; Li, Lin; Xu, Xiandong; Rawlings, Michael; Liebscher, Christian H.; Clausen, Bjørn; Poplawsky, Jonathan; Leonard, Donovan N.; Huang, Shenyan; Teng, Zhenke; Liu, Chain T.; Asta, Mark D.; Gao, Yanfei; Dunand, David C.; Ghosh, Gautam; Chen, Mingwei; Fine, Morris E.; Liaw, Peter K.

2015-01-01

There have been numerous efforts to develop creep-resistant materials strengthened by incoherent particles at high temperatures and stresses in response to future energy needs for steam turbines in thermal-power plants. However, the microstructural instability of the incoherent-particle-strengthened ferritic steels limits their application to temperatures below 900 K. Here, we report a novel ferritic alloy with the excellent creep resistance enhanced by coherent hierarchical precipitates, using the integrated experimental (transmission-electron microscopy/scanning-transmission-electron microscopy, in-situ neutron diffraction, and atom-probe tomography) and theoretical (crystal-plasticity finite-element modeling) approaches. This alloy is strengthened by nano-scaled L21-Ni2TiAl (Heusler phase)-based precipitates, which themselves contain coherent nano-scaled B2 zones. These coherent hierarchical precipitates are uniformly distributed within the Fe matrix. Our hierarchical structure material exhibits the superior creep resistance at 973 K in terms of the minimal creep rate, which is four orders of magnitude lower than that of conventional ferritic steels. These results provide a new alloy-design strategy using the novel concept of hierarchical precipitates and the fundamental science for developing creep-resistant ferritic alloys. The present research will broaden the applications of ferritic alloys to higher temperatures. PMID:26548303

Ferritic Alloys with Extreme Creep Resistance via Coherent Hierarchical Precipitates

DOE PAGES

Song, Gian; Sun, Zhiqian; Li, Lin; ...

2015-11-09

There have been numerous efforts to develop creep-resistant materials strengthened by incoherent particles at high temperatures and stresses in response to future energy needs for steam turbines in thermal-power plants. However, the microstructural instability of the incoherent-particle-strengthened ferritic steels limits their application to temperatures below 900 K. Here, we report a novel ferritic alloy with the excellent creep resistance enhanced by coherent hierarchical precipitates, using the integrated experimental (transmission-electron microscopy/scanning-transmission-electron microscopy, in-situ neutron diffraction, and atom-probe tomography) and theoretical (crystal-plasticity finite-element modeling) approaches. This alloy is strengthened by nano-scaled L21-Ni2TiAl (Heusler phase)-based precipitates, which themselves contain coherent nano-scaled B2 zones.more » These coherent hierarchical precipitates are uniformly distributed within the Fe matrix. Our hierarchical structure material exhibits the superior creep resistance at 973 K in terms of the minimal creep rate, which is four orders of magnitude lower than that of conventional ferritic steels. These results provide a new alloy-design strategy using the novel concept of hierarchical precipitates and the fundamental science for developing creep-resistant ferritic alloys. Finally, the present research will broaden the applications of ferritic alloys to higher temperatures.« less

Cybermaterials: materials by design and accelerated insertion of materials

NASA Astrophysics Data System (ADS)

Xiong, Wei; Olson, Gregory B.

2016-02-01

Cybermaterials innovation entails an integration of Materials by Design and accelerated insertion of materials (AIM), which transfers studio ideation into industrial manufacturing. By assembling a hierarchical architecture of integrated computational materials design (ICMD) based on materials genomic fundamental databases, the ICMD mechanistic design models accelerate innovation. We here review progress in the development of linkage models of the process-structure-property-performance paradigm, as well as related design accelerating tools. Extending the materials development capability based on phase-level structural control requires more fundamental investment at the level of the Materials Genome, with focus on improving applicable parametric design models and constructing high-quality databases. Future opportunities in materials genomic research serving both Materials by Design and AIM are addressed.

Nanotwinned and hierarchical nanotwinned metals: a review of experimental, computational and theoretical efforts

NASA Astrophysics Data System (ADS)

Sun, Ligang; He, Xiaoqiao; Lu, Jian

2018-02-01

The recent studies on nanotwinned (NT) and hierarchical nanotwinned (HNT) face-centered cubic (FCC) metals are presented in this review. The HNT structures have been supposed as a kind of novel structure to bring about higher strength/ductility than NT counterparts in crystalline materials. We primarily focus on the recent developments of the experimental, atomistic and theoretical studies on the NT and HNT structures in the metallic materials. Some advanced bottom-up and top-down techniques for the fabrication of NT and HNT structures are introduced. The deformation induced HNT structures are available by virtue of severe plastic deformation (SPD) based techniques while the synthesis of growth HNT structures is so far almost unavailable. In addition, some representative molecular dynamics (MD) studies on the NT and HNT FCC metals unveil that the nanoscale effects such as twin spacing, grain size and plastic anisotropy greatly alter the performance of NT and HNT metals. The HNT structures may initiate unique phenomena in comparison with the NT ones. Furthermore, based on the phenomena and mechanisms revealed by experimental and MD simulation observations, a series of theoretical models have been proposed. They are effective to describe the mechanical behaviors of NT and HNT metals within the applicable scope. So far the development of manufacturing technologies of HNT structures, as well as the studies on the effects of HNT structures on the properties of metals are still in its infancy. Further exploration is required to promote the design of advanced materials.

Hierarchical micro-architectures of electrodes for energy storage

NASA Astrophysics Data System (ADS)

Yue, Yuan; Liang, Hong

2015-06-01

The design of electrodes for the electrochemical energy storage devices, particularly Lithium ion batteries (LIBs) and Supercapacitors (SCs), has extraordinary importance in optimization of electrochemical performance. Regardless of the materials used, the architecture of electrodes is crucial for charge transport efficiency and electrochemical interactions. This report provides a critical review of the prototype architectural design and micro- and nano-material properties designated to electrodes of LIBs and SCs. An alternative classification criterion is proposed that divides reported hierarchical architectures into two categories: aligned and unaligned structures. The structures were evaluated and it was found that the aligned architectures are superior to the unaligned in the following characteristics: 1) highly-organized charger pathways, 2) tunable interspaces between architecture units, and 3) good electric-contacted current collectors prepared along with electrodes. Based on these findings, challenges and potential routes to resolve those are provided for future development.

Chiral nematic self-assembly of minimally surface damaged chitin nanofibrils and its load bearing functions

NASA Astrophysics Data System (ADS)

Oh, Dongyeop X.; Cha, Yun Jeong; Nguyen, Hoang-Linh; Je, Hwa Heon; Jho, Yong Seok; Hwang, Dong Soo; Yoon, Dong Ki

2016-03-01

Chitin is one of the most abundant biomaterials in nature, with 1010 tons produced annually as hierarchically organized nanofibril fillers to reinforce the exoskeletons of arthropods. This green and cheap biomaterial has attracted great attention due to its potential application to reinforce biomedical materials. Despite that, its practical use is limited since the extraction of chitin nanofibrils requires surface modification involving harsh chemical treatments, leading to difficulties in reproducing their natural prototypal hierarchical structure, i.e. chiral nematic phase. Here, we develop a chemical etching-free approach using calcium ions, called “natural way”, to disintegrate the chitin nanofibrils while keeping the essential moiety for the self-assembly, ultimately resulting in the reproduction of chitin’s natural chiral structure in a polymeric matrix. This chiral chitin nanostructure exceptionally toughens the composite. Our resultant chiral nematic phase of chitin materials can contribute to the understanding and use of the reinforcing strategy in nature.

Enhanced protective role in materials with gradient structural orientations: Lessons from Nature.

PubMed

Liu, Zengqian; Zhu, Yankun; Jiao, Da; Weng, Zhaoyong; Zhang, Zhefeng; Ritchie, Robert O

2016-10-15

Living organisms are adept at resisting contact deformation and damage by assembling protective surfaces with spatially varied mechanical properties, i.e., by creating functionally graded materials. Such gradients, together with multiple length-scale hierarchical structures, represent the two prime characteristics of many biological materials to be translated into engineering design. Here, we examine one design motif from a variety of biological tissues and materials where site-specific mechanical properties are generated for enhanced protection by adopting gradients in structural orientation over multiple length-scales, without manipulation of composition or microstructural dimension. Quantitative correlations are established between the structural orientations and local mechanical properties, such as stiffness, strength and fracture resistance; based on such gradients, the underlying mechanisms for the enhanced protective role of these materials are clarified. Theoretical analysis is presented and corroborated through numerical simulations of the indentation behavior of composites with distinct orientations. The design strategy of such bioinspired gradients is outlined in terms of the geometry of constituents. This study may offer a feasible approach towards generating functionally graded mechanical properties in synthetic materials for improved contact damage resistance. Living organisms are adept at resisting contact damage by assembling protective surfaces with spatially varied mechanical properties, i.e., by creating functionally-graded materials. Such gradients, together with multiple length-scale hierarchical structures, represent the prime characteristics of many biological materials. Here, we examine one design motif from a variety of biological tissues where site-specific mechanical properties are generated for enhanced protection by adopting gradients in structural orientation at multiple length-scales, without changes in composition or microstructural dimension. The design strategy of such bioinspired gradients is outlined in terms of the geometry of constituents. This study may offer a feasible approach towards generating functionally-graded mechanical properties in synthetic materials for improved damage resistance. Published by Elsevier Ltd.

Block Copolymer Directed Biomimetic Mineral Formation for Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Gleeson, Sarah; Yu, Tony; Chen, Xi; Marcolongo, Michele; Li, Christopher

Bone is a hierarchically structured biocomposite comprised of mineralized collagen fibrils. The mechanical properties of bone can be precisely tuned by the structure and morphology of the mineral nanocrystals as well as the organic collagen fibrils. Synthetic materials that can mimic the nanostructure of natural bone show promise to replicate bone's structural function, yet little is known about the mechanism of mineral formation. We previously have shown that hierarchically ordered polymer fibers control the distribution and orientation of hydroxyapatite, enhancing mechanical properties and biocompatibility. We demonstrate a new method for mineralization by forming block copolymer single crystal films of polycaprolactone-block-poly(acrylic acid) (PCL- b-PAA) so that lamellar anionic PAA nanodomains recruit mineral ions and provide one-dimensional confinement to induce orientation. The effect of the anionic domain dimensions on mineral content, orientation, and structure within the polymer matrix is shown. The mechanical properties of the nanocomposite are evaluated to determine the role of mineral orientation and crystallinity in composite strength. These results can be used to tailor the physical mineralization environment to create a more biomimetic bone material.

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

DOE PAGES

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; ...

2017-11-13

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

PubMed Central

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; Yang, Lin; Yoshimura, Hideyuki; Miettinen, Heini M.; LaFrance, Ben; Patterson, Dustin P.; Schwarz, Benjamin; Karty, Jonathan A.; Prevelige, Peter E.; Lee, Byeongdu; Douglas, Trevor

2018-01-01

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy; the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from an amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles, and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. This study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales, and exhibits properties and function that arise from the interaction between individual building blocks. PMID:29131580

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

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

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

Segmented molecular design of self-healing proteinaceous materials

NASA Astrophysics Data System (ADS)

Sariola, Veikko; Pena-Francesch, Abdon; Jung, Huihun; Çetinkaya, Murat; Pacheco, Carlos; Sitti, Metin; Demirel, Melik C.

2015-09-01

Hierarchical assembly of self-healing adhesive proteins creates strong and robust structural and interfacial materials, but understanding of the molecular design and structure-property relationships of structural proteins remains unclear. Elucidating this relationship would allow rational design of next generation genetically engineered self-healing structural proteins. Here we report a general self-healing and -assembly strategy based on a multiphase recombinant protein based material. Segmented structure of the protein shows soft glycine- and tyrosine-rich segments with self-healing capability and hard beta-sheet segments. The soft segments are strongly plasticized by water, lowering the self-healing temperature close to body temperature. The hard segments self-assemble into nanoconfined domains to reinforce the material. The healing strength scales sublinearly with contact time, which associates with diffusion and wetting of autohesion. The finding suggests that recombinant structural proteins from heterologous expression have potential as strong and repairable engineering materials.

Segmented molecular design of self-healing proteinaceous materials.

PubMed

Sariola, Veikko; Pena-Francesch, Abdon; Jung, Huihun; Çetinkaya, Murat; Pacheco, Carlos; Sitti, Metin; Demirel, Melik C

2015-09-01

Hierarchical assembly of self-healing adhesive proteins creates strong and robust structural and interfacial materials, but understanding of the molecular design and structure-property relationships of structural proteins remains unclear. Elucidating this relationship would allow rational design of next generation genetically engineered self-healing structural proteins. Here we report a general self-healing and -assembly strategy based on a multiphase recombinant protein based material. Segmented structure of the protein shows soft glycine- and tyrosine-rich segments with self-healing capability and hard beta-sheet segments. The soft segments are strongly plasticized by water, lowering the self-healing temperature close to body temperature. The hard segments self-assemble into nanoconfined domains to reinforce the material. The healing strength scales sublinearly with contact time, which associates with diffusion and wetting of autohesion. The finding suggests that recombinant structural proteins from heterologous expression have potential as strong and repairable engineering materials.

Hierarchically nanostructured materials for sustainable environmental applications

PubMed Central

Ren, Zheng; Guo, Yanbing; Liu, Cai-Hong; Gao, Pu-Xian

2013-01-01

This review presents a comprehensive overview of the hierarchical nanostructured materials with either geometry or composition complexity in environmental applications. The hierarchical nanostructures offer advantages of high surface area, synergistic interactions, and multiple functionalities toward water remediation, biosensing, environmental gas sensing and monitoring as well as catalytic gas treatment. Recent advances in synthetic strategies for various hierarchical morphologies such as hollow spheres and urchin-shaped architectures have been reviewed. In addition to the chemical synthesis, the physical mechanisms associated with the materials design and device fabrication have been discussed for each specific application. The development and application of hierarchical complex perovskite oxide nanostructures have also been introduced in photocatalytic water remediation, gas sensing, and catalytic converter. Hierarchical nanostructures will open up many possibilities for materials design and device fabrication in environmental chemistry and technology. PMID:24790946

Hierarchically Nanostructured Materials for Sustainable Environmental Applications

NASA Astrophysics Data System (ADS)

Ren, Zheng; Guo, Yanbing; Liu, Cai-Hong; Gao, Pu-Xian

2013-11-01

This article presents a comprehensive overview of the hierarchical nanostructured materials with either geometry or composition complexity in environmental applications. The hierarchical nanostructures offer advantages of high surface area, synergistic interactions and multiple functionalities towards water remediation, environmental gas sensing and monitoring as well as catalytic gas treatment. Recent advances in synthetic strategies for various hierarchical morphologies such as hollow spheres and urchin-shaped architectures have been reviewed. In addition to the chemical synthesis, the physical mechanisms associated with the materials design and device fabrication have been discussed for each specific application. The development and application of hierarchical complex perovskite oxide nanostructures have also been introduced in photocatalytic water remediation, gas sensing and catalytic converter. Hierarchical nanostructures will open up many possibilities for materials design and device fabrication in environmental chemistry and technology.

Rational Design of Hierarchically Core-Shell Structured Ni3 S2 @NiMoO4 Nanowires for Electrochemical Energy Storage.

PubMed

Chen, Fangshuai; Ji, Shan; Liu, Quanbing; Wang, Hui; Liu, Hao; Brett, Dan J L; Wang, Guoxiu; Wang, Rongfang

2018-05-30

Rational design and controllable synthesis of nanostructured materials with unique microstructure and excellent electrochemical performance for energy storage are crucially desired. In this paper, a facile method is reported for general synthesis of hierarchically core-shell structured Ni 3 S 2 @NiMoO 4 nanowires (NWs) as a binder-free electrode for asymmetric supercapacitors. Due to the intimate contact between Ni 3 S 2 and NiMoO 4 , the hierarchical structured electrodes provide a promising unique structure for asymmetric supercapacitors. The as-prepared binder-free Ni 3 S 2 @NiMoO 4 electrode can significantly improve the electrical conductivity between Ni 3 S 2 and NiMoO 4 , and effectively avoid the aggregation of NiMoO 4 nanosheets, which provide more active space for storing charge. The Ni 3 S 2 @NiMoO 4 electrode presents a high areal capacity of 1327.3 µAh cm -2 and 67.8% retention of its initial capacity when current density increases from 2 to 40 mA cm -2 . In a two-electrode Ni 3 S 2 @NiMoO 4 //active carbon cell, the active materials deliver a high energy density of 121.5 Wh kg -1 at a power density of 2.285 kW kg -1 with excellent cycling stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Layered nanocomposites inspired by the structure and mechanical properties of nacre.

PubMed

Wang, Jianfeng; Cheng, Qunfeng; Tang, Zhiyong

2012-02-07

Nacre (mother-of-pearl), made of inorganic and organic constituents (95 vol% aragonite calcium carbonate (CaCO(3)) platelets and 5 vol% elastic biopolymers), possesses a unique combination of remarkable strength and toughness, which is compatible for conventional high performance materials. The excellent mechanical properties are related to its hierarchical structure and precisely designed organic-inorganic interface. The rational design of aragonite platelet strength, aspect ratio of aragonite platelets, and interface strength ensures that the strength of nacre is maximized under platelet pull-out failure mode. At the same time, the synergy of strain hardening mechanisms acting over multiple scales results in platelets sliding on one another, and thus maximizes the energy dissipation of viscoplastic biopolymers. The excellent integrated mechanical properties with hierarchical structure have inspired chemists and materials scientists to develop biomimetic strategies for artificial nacre materials. This critical review presents a broad overview of the state-of-the-art work on the preparation of layered organic-inorganic nanocomposites inspired by nacre, in particular, the advantages and disadvantages of various biomimetic strategies. Discussion is focused on the effect of the layered structure, interface, and component loading on strength and toughness of nacre-mimic layered nanocomposites (148 references). This journal is © The Royal Society of Chemistry 2012

Synthesis of flower-like BaTiO3/Fe3O4 hierarchically structured particles and their electrorheological and magnetic properties.

PubMed

Wang, Baoxiang; Yin, Yichao; Liu, Chenjie; Yu, Shoushan; Chen, Kezheng

2013-07-21

Flower-like BaTiO3/Fe3O4 hierarchically structured particles composed of nano-scale structures on micro-scale materials were synthesized by a simple solvothermal approach and characterized by the means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), magnetic testing and rotary viscometer. The influences on the morphology and structure of solvothermal times, type and amount of surfactant, EG : H2O ratio, etc. were studied. Magnetic testing results show that the samples have strong magnetism and they exhibit superparamagnetic behavior, as evidenced by no coercivity and the remanence at room temperature, due to their very small sizes, observed on the M-H loop. The saturation magnetization (M(s)) value can achieve 18.3 emu g(-1). The electrorheological (ER) effect was investigated using a suspension of the flower-like BaTiO3/Fe3O4 hierarchically structured particles dispersed in silicone oil. We can observe a slight shear-thinning behavior of shear viscosity at a low shear rate region even at zero applied electric field and a Newtonian fluid behavior at high shear rate regions.

One-step hydrothermal synthesis of feather duster-like NiS@MoS2 with hierarchical array structure for the Pt-free dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Su, Lijun; Xiao, Yaoming; Han, Gaoyi; Lin, Jeng-Yu

2018-04-01

Novel feather duster-like nickel sulfide (NiS) @ molybdenum sulfide (MoS2) with hierarchical array structure is synthesized via a simple one-step hydrothermal method, in which a major structure of rod-like NiS in the center and a secondary structure of MoS2 nanosheets with a thickness of about 15-55 nm on the surface. The feather duster-like NiS@MoS2 is employed as the counter electrode (CE) material for the dye-sensitized solar cell (DSSC), which exhibits superior electrocatalytic activity due to its feather duster-like hierarchical array structure can not only support the fast electron transfer and electrolyte diffusion channels, but also can provide high specific surface area (238.19 m2 g-1) with abundant active catalytic sites and large electron injection efficiency from CE to electrolyte. The DSSC based on the NiS@MoS2 CE achieves a competitive photoelectric conversion efficiency of 8.58%, which is higher than that of the NiS (7.13%), MoS2 (7.33%), and Pt (8.16%) CEs under the same conditions. [Figure not available: see fulltext.

Hierarchically structured MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Sun, Zhipeng; Firdoz, Shaik; Ying-Xuan Yap, Esther; Li, Lan; Lu, Xianmao

2013-05-01

We report a hierarchical Ni@MnO2 structure consisting of MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors. The Ni@MnO2 structure, which was prepared via a facile electrodeposition method, is highly porous and appears like a forest of pine trees grown vertically on a substrate. At a MnO2 mass loading of 0.35 mg cm-2, the Ni@MnO2 electrode demonstrated a specific capacitance of 1125 F g-1 that is close to the theoretical value. In addition, a remarkable high-rate performance (766 F g-1 at a discharge current density of 100 A g-1) was achieved. Electrochemical tests in a two-electrode configuration for the Ni@MnO2 structure with a high MnO2 loading of 3.6 mg cm-2 showed a low equivalent series resistance (ESR) of 1 Ω and a high specific power of 72 kW kg-1. This superior performance can be attributed to the highly porous and hierarchical structure of Ni@MnO2 that favors rapid diffusion of an electrolyte, highly conductive pathway for electron transport, and efficient material utilization.We report a hierarchical Ni@MnO2 structure consisting of MnO2 nanowires supported on hollow Ni dendrites for high-performance supercapacitors. The Ni@MnO2 structure, which was prepared via a facile electrodeposition method, is highly porous and appears like a forest of pine trees grown vertically on a substrate. At a MnO2 mass loading of 0.35 mg cm-2, the Ni@MnO2 electrode demonstrated a specific capacitance of 1125 F g-1 that is close to the theoretical value. In addition, a remarkable high-rate performance (766 F g-1 at a discharge current density of 100 A g-1) was achieved. Electrochemical tests in a two-electrode configuration for the Ni@MnO2 structure with a high MnO2 loading of 3.6 mg cm-2 showed a low equivalent series resistance (ESR) of 1 Ω and a high specific power of 72 kW kg-1. This superior performance can be attributed to the highly porous and hierarchical structure of Ni@MnO2 that favors rapid diffusion of an electrolyte, highly conductive pathway for electron transport, and efficient material utilization. Electronic supplementary information (ESI) available: More TEM and SEM images, digital photo, XPS, and XRD of the samples. See DOI: 10.1039/c3nr00209h

Facile Synthesis of Nitrogen and Oxygen Co-Doped Clews of Carbon Nanobelts for Supercapacitors with Excellent Rate Performance.

PubMed

Yu, Liang; Zeng, Shaozhong; Zeng, Xierong; Li, Xiaohua; Wu, Hongliang; Yao, Yuechao; Tu, Wenxuan; Zou, Jizhao

2018-04-04

Facile synthesis of carbon materials with high heteroatom content, large specific surface area (SSA) and hierarchical porous structure is critical for energy storage applications. In this study, nitrogen and oxygen co-doped clews of carbon nanobelts (NCNBs) with hierarchical porous structures are successfully prepared by a carbonization and subsequent activation by using ladder polymer of hydroquinone and formaldehyde (LPHF) as the precursor and ammonia as the activating agent. The hierarchical porous structures and ultra-high SSA (up to 2994 m² g −1 ) can effectively facilitate the exchange and transportation of electrons and ions. Moreover, suitable heteroatom content is believed to modify the wettability of the carbon material. The as-prepared activated NCNBs-60 (the NCNBs activated by ammonia at 950 °C for 60 min) possess a high capacitance of 282 F g −1 at the current density of 0.25 A g −1 , NCNBs-45 (the NCNBs are activated by ammonia at 950 °C for 45 min) and show an excellent capacity retention of 50.2% when the current density increase from 0.25 to 150 A g −1 . Moreover, the NCNBs-45 electrode exhibits superior electrochemical stability with 96.2% capacity retention after 10,000 cycles at 5.0 A g −1 . The newly prepared NCNBs thus show great potential in the field of energy storage.

Facile Synthesis of Nitrogen and Oxygen Co-Doped Clews of Carbon Nanobelts for Supercapacitors with Excellent Rate Performance

PubMed Central

Yu, Liang; Zeng, Shaozhong; Zeng, Xierong; Li, Xiaohua; Wu, Hongliang; Yao, Yuechao; Tu, Wenxuan; Zou, Jizhao

2018-01-01

Facile synthesis of carbon materials with high heteroatom content, large specific surface area (SSA) and hierarchical porous structure is critical for energy storage applications. In this study, nitrogen and oxygen co-doped clews of carbon nanobelts (NCNBs) with hierarchical porous structures are successfully prepared by a carbonization and subsequent activation by using ladder polymer of hydroquinone and formaldehyde (LPHF) as the precursor and ammonia as the activating agent. The hierarchical porous structures and ultra-high SSA (up to 2994 m2 g−1) can effectively facilitate the exchange and transportation of electrons and ions. Moreover, suitable heteroatom content is believed to modify the wettability of the carbon material. The as-prepared activated NCNBs-60 (the NCNBs activated by ammonia at 950 °C for 60 min) possess a high capacitance of 282 F g−1 at the current density of 0.25 A g−1, NCNBs-45 (the NCNBs are activated by ammonia at 950 °C for 45 min) and show an excellent capacity retention of 50.2% when the current density increase from 0.25 to 150 A g−1. Moreover, the NCNBs-45 electrode exhibits superior electrochemical stability with 96.2% capacity retention after 10,000 cycles at 5.0 A g−1. The newly prepared NCNBs thus show great potential in the field of energy storage. PMID:29617315

Hierarchical MoS2-coated three-dimensional graphene network for enhanced supercapacitor performances

NASA Astrophysics Data System (ADS)

Zhou, Rui; Han, Cheng-jie; Wang, Xiao-min

2017-06-01

Layered molybdenum disulfide (MoS2) owns graphene-like two-dimensional structure, and when used as the electrode material for energy storage devices, the intercalation of electrolyte ions is permitted. Herein, a simple dipping and drying method is employed to stack few-layered MoS2 nanosheets on a three-dimensional graphene network (3DGN). The structure measurement results indicate that the assembled hierarchical MoS2 nanosheets own expanded interlayer spacing (∼0.75 nm) and are stacked on the surface of 3DGN uncontinuously. The composite can achieve 110.57% capacitance retention after 4000 cycles of galvanostatic charge/discharge tests and 76.73% capacitance retention with increasing the current density from 1 A g-1 to 100 A g-1. Moreover, the asymmetric coin cell supercapacitor using MoS2@3DGN and active carbon as electrode materials is assembled. This device could achieve a working voltage window of 1.6 V along with the power and energy densities of 400.0-8001.6 W kg-1 and 36.43-1.12 Wh kg-1 respectively. The enhanced electrochemical performance can be attributed to: (1) the expanded interlayer spacing of hierarchical MoS2 nanosheets which can facilitate the fast intercalation/deintercalation of electrolyte cations, (2) the uncontinuous deposition of hierarchical MoS2 nanosheets which facilitates more contact between electrolyte and the section of MoS2 nanosheets to provide more gates for the intercalation/deintercalation.

Converting Corncob to Activated Porous Carbon for Supercapacitor Application.

PubMed

Yang, Shaoran; Zhang, Kaili

2018-03-21

Carbon materials derived from biomass are promising electrode materials for supercapacitor application due to their specific porosity, low cost and electrochemical stability. Herein, a hierarchical porous carbon derived from corncob was developed for use as electrodes. Benefitting from its hierarchical porosity, inherited from the natural structure of corncob, high BET surface area (1471.4 m²·g -1 ) and excellent electrical conductivity, the novel carbon material exhibited a specific capacitance of 293 F·g -1 at 1 A·g -1 in 6 M KOH electrolyte and maintained at 195 F·g -1 at 5 A·g -1 . In addition, a two-electrode device was assembled and delivered an energy density of 20.15 Wh·kg -1 at a power density of 500 W·kg -1 and an outstanding stability of 99.9% capacitance retention after 4000 cycles.

Multi-scale modelling of elastic moduli of trabecular bone

PubMed Central

Hamed, Elham; Jasiuk, Iwona; Yoo, Andrew; Lee, YikHan; Liszka, Tadeusz

2012-01-01

We model trabecular bone as a nanocomposite material with hierarchical structure and predict its elastic properties at different structural scales. The analysis involves a bottom-up multi-scale approach, starting with nanoscale (mineralized collagen fibril) and moving up the scales to sub-microscale (single lamella), microscale (single trabecula) and mesoscale (trabecular bone) levels. Continuum micromechanics methods, composite materials laminate theory and finite-element methods are used in the analysis. Good agreement is found between theoretical and experimental results. PMID:22279160

Segmented molecular design of self-healing proteinaceous materials

PubMed Central

Sariola, Veikko; Pena-Francesch, Abdon; Jung, Huihun; Çetinkaya, Murat; Pacheco, Carlos; Sitti, Metin; Demirel, Melik C.

2015-01-01

Hierarchical assembly of self-healing adhesive proteins creates strong and robust structural and interfacial materials, but understanding of the molecular design and structure–property relationships of structural proteins remains unclear. Elucidating this relationship would allow rational design of next generation genetically engineered self-healing structural proteins. Here we report a general self-healing and -assembly strategy based on a multiphase recombinant protein based material. Segmented structure of the protein shows soft glycine- and tyrosine-rich segments with self-healing capability and hard beta-sheet segments. The soft segments are strongly plasticized by water, lowering the self-healing temperature close to body temperature. The hard segments self-assemble into nanoconfined domains to reinforce the material. The healing strength scales sublinearly with contact time, which associates with diffusion and wetting of autohesion. The finding suggests that recombinant structural proteins from heterologous expression have potential as strong and repairable engineering materials. PMID:26323335

Hierarchical polymerized high internal phase emulsions synthesized from surfactant-stabilized emulsion templates.

PubMed

Wong, Ling L C; Villafranca, Pedro M Baiz; Menner, Angelika; Bismarck, Alexander

2013-05-21

In building construction, structural elements, such as lattice girders, are positioned specifically to support the mainframe of a building. This arrangement provides additional structural hierarchy, facilitating the transfer of load to its foundation while keeping the building weight down. We applied the same concept when synthesizing hierarchical open-celled macroporous polymers from high internal phase emulsion (HIPE) templates stabilized by varying concentrations of a polymeric non-ionic surfactant from 0.75 to 20 w/vol %. These hierarchical poly(merized)HIPEs have multimodally distributed pores, which are efficiently arranged to enhance the load transfer mechanism in the polymer foam. As a result, hierarchical polyHIPEs produced from HIPEs stabilized by 5 vol % surfactant showed a 93% improvement in Young's moduli compared to conventional polyHIPEs produced from HIPEs stabilized by 20 vol % of surfactant with the same porosity of 84%. The finite element method (FEM) was used to determine the effect of pore hierarchy on the mechanical performance of porous polymers under small periodic compressions. Results from the FEM showed a clear improvement in Young's moduli for simulated hierarchical porous geometries. This methodology could be further adapted as a predictive tool to determine the influence of hierarchy on the mechanical properties of a range of porous materials.

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

Song, Gian; Sun, Zhiqian; Li, Lin

There have been numerous efforts to develop creep-resistant materials strengthened by incoherent particles at high temperatures and stresses in response to future energy needs for steam turbines in thermal-power plants. However, the microstructural instability of the incoherent-particle-strengthened ferritic steels limits their application to temperatures below 900 K. Here, we report a novel ferritic alloy with the excellent creep resistance enhanced by coherent hierarchical precipitates, using the integrated experimental (transmission-electron microscopy/scanning-transmission-electron microscopy, in-situ neutron diffraction, and atom-probe tomography) and theoretical (crystal-plasticity finite-element modeling) approaches. This alloy is strengthened by nano-scaled L21-Ni2TiAl (Heusler phase)-based precipitates, which themselves contain coherent nano-scaled B2 zones.more » These coherent hierarchical precipitates are uniformly distributed within the Fe matrix. Our hierarchical structure material exhibits the superior creep resistance at 973 K in terms of the minimal creep rate, which is four orders of magnitude lower than that of conventional ferritic steels. These results provide a new alloy-design strategy using the novel concept of hierarchical precipitates and the fundamental science for developing creep-resistant ferritic alloys. Finally, the present research will broaden the applications of ferritic alloys to higher temperatures.« less

Resilient 3D hierarchical architected metamaterials

PubMed Central

Meza, Lucas R.; Zelhofer, Alex J.; Clarke, Nigel; Mateos, Arturo J.; Kochmann, Dennis M.; Greer, Julia R.

2015-01-01

Hierarchically designed structures with architectural features that span across multiple length scales are found in numerous hard biomaterials, like bone, wood, and glass sponge skeletons, as well as manmade structures, like the Eiffel Tower. It has been hypothesized that their mechanical robustness and damage tolerance stem from sophisticated ordering within the constituents, but the specific role of hierarchy remains to be fully described and understood. We apply the principles of hierarchical design to create structural metamaterials from three material systems: (i) polymer, (ii) hollow ceramic, and (iii) ceramic–polymer composites that are patterned into self-similar unit cells in a fractal-like geometry. In situ nanomechanical experiments revealed (i) a nearly theoretical scaling of structural strength and stiffness with relative density, which outperforms existing nonhierarchical nanolattices; (ii) recoverability, with hollow alumina samples recovering up to 98% of their original height after compression to ≥50% strain; (iii) suppression of brittle failure and structural instabilities in hollow ceramic hierarchical nanolattices; and (iv) a range of deformation mechanisms that can be tuned by changing the slenderness ratios of the beams. Additional levels of hierarchy beyond a second order did not increase the strength or stiffness, which suggests the existence of an optimal degree of hierarchy to amplify resilience. We developed a computational model that captures local stress distributions within the nanolattices under compression and explains some of the underlying deformation mechanisms as well as validates the measured effective stiffness to be interpreted as a metamaterial property. PMID:26330605

Resilient 3D hierarchical architected metamaterials.

PubMed

Meza, Lucas R; Zelhofer, Alex J; Clarke, Nigel; Mateos, Arturo J; Kochmann, Dennis M; Greer, Julia R

2015-09-15

Hierarchically designed structures with architectural features that span across multiple length scales are found in numerous hard biomaterials, like bone, wood, and glass sponge skeletons, as well as manmade structures, like the Eiffel Tower. It has been hypothesized that their mechanical robustness and damage tolerance stem from sophisticated ordering within the constituents, but the specific role of hierarchy remains to be fully described and understood. We apply the principles of hierarchical design to create structural metamaterials from three material systems: (i) polymer, (ii) hollow ceramic, and (iii) ceramic-polymer composites that are patterned into self-similar unit cells in a fractal-like geometry. In situ nanomechanical experiments revealed (i) a nearly theoretical scaling of structural strength and stiffness with relative density, which outperforms existing nonhierarchical nanolattices; (ii) recoverability, with hollow alumina samples recovering up to 98% of their original height after compression to ≥ 50% strain; (iii) suppression of brittle failure and structural instabilities in hollow ceramic hierarchical nanolattices; and (iv) a range of deformation mechanisms that can be tuned by changing the slenderness ratios of the beams. Additional levels of hierarchy beyond a second order did not increase the strength or stiffness, which suggests the existence of an optimal degree of hierarchy to amplify resilience. We developed a computational model that captures local stress distributions within the nanolattices under compression and explains some of the underlying deformation mechanisms as well as validates the measured effective stiffness to be interpreted as a metamaterial property.

Superhydrophobic Surface Based on a Coral-Like Hierarchical Structure of ZnO

PubMed Central

Wu, Jun; Xia, Jun; Lei, Wei; Wang, Baoping

2010-01-01

Background Fabrication of superhydrophobic surfaces has attracted much interest in the past decade. The fabrication methods that have been studied are chemical vapour deposition, the sol-gel method, etching technique, electrochemical deposition, the layer-by-layer deposition, and so on. Simple and inexpensive methods for manufacturing environmentally stable superhydrophobic surfaces have also been proposed lately. However, work referring to the influence of special structures on the wettability, such as hierarchical ZnO nanostructures, is rare. Methodology This study presents a simple and reproducible method to fabricate a superhydrophobic surface with micro-scale roughness based on zinc oxide (ZnO) hierarchical structure, which is grown by the hydrothermal method with an alkaline aqueous solution. Coral-like structures of ZnO were fabricated on a glass substrate with a micro-scale roughness, while the antennas of the coral formed the nano-scale roughness. The fresh ZnO films exhibited excellent superhydrophilicity (the apparent contact angle for water droplet was about 0°), while the ability to be wet could be changed to superhydrophobicity after spin-coating Teflon (the apparent contact angle greater than 168°). The procedure reported here can be applied to substrates consisting of other materials and having various shapes. Results The new process is convenient and environmentally friendly compared to conventional methods. Furthermore, the hierarchical structure generates the extraordinary solid/gas/liquid three-phase contact interface, which is the essential characteristic for a superhydrophobic surface. PMID:21209931

Sphere-Shaped Hierarchical Cathode with Enhanced Growth of Nanocrystal Planes for High-Rate and Cycling-Stable Li-Ion Batteries

DOE PAGES

Zhang, Linjing; Li, Ning; Wu, Borong; ...

2015-01-14

High-energy and high-power Li-ion batteries have been intensively pursued as power sources in electronic vehicles and renewable energy storage systems in smart grids. With this purpose, developing high-performance cathode materials is urgently needed. Here we report an easy and versatile strategy to fabricate high-rate and cycling-stable hierarchical sphered cathode Li 1.2Ni 0.13Mn 0.54Co 0.13O 2, by using an ionic interfusion method. The sphere-shaped hierarchical cathode is assembled with primary nanoplates with enhanced growth of nanocrystal planes in favor of Li+ intercalation/deintercalation, such as (010), (100), and (110) planes. This material with such unique structural features exhibits outstanding rate capability, cyclability,more » and high discharge capacities, achieving around 70% (175 mAh g–1) of the capacity at 0.1 C rate within about 2.1 min of ultrafast charging. Such cathode is feasible to construct high-energy and high-power Li-ion batteries.« less

IR and NMR studies of hierarchical material obtained by the treatment of zeolite Y by ammonia solution

NASA Astrophysics Data System (ADS)

Gackowski, Mariusz; Kuterasiński, Łukasz; Podobiński, Jerzy; Sulikowski, Bogdan; Datka, Jerzy

2018-03-01

Ammonia treatment of ultrastable zeolite Y has a great impact on its features. XRD showed a partial loss of crystallinity coupled with a loss of long-distance zeolite ordering. However, a typical short-range zeolite ordering, in the light of 29Si NMR studies, was largely preserved. 27Al MAS NMR spectra evidenced that most of Al was located in zeolitic tetrahedral positions, but some of them adopted a distorted configuration. Evolution of zeolites acidity was followed quantitatively by using IR. In particular, such studies revealed the presence of strongly acidic Sisbnd OHsbnd Al groups. IR studies suggest also heterogeneity of these OH groups. The heterogeneity of Sisbnd OHsbnd Al groups was a consequence of the less ordered structure of zeolites treated with ammonia solutions. It was also found that the treatment with ammonia solutions yields hierarchical material. The samples revealed promising catalytic properties in the liquid phase isomerization of α-pinene. Zeolites desilicated with ammonia may constitute an inexpensive route yielding viable hierarchical catalysts.

Sphere-shaped hierarchical cathode with enhanced growth of nanocrystal planes for high-rate and cycling-stable li-ion batteries.

PubMed

Zhang, Linjing; Li, Ning; Wu, Borong; Xu, Hongliang; Wang, Lei; Yang, Xiao-Qing; Wu, Feng

2015-01-14

High-energy and high-power Li-ion batteries have been intensively pursued as power sources in electronic vehicles and renewable energy storage systems in smart grids. With this purpose, developing high-performance cathode materials is urgently needed. Here we report an easy and versatile strategy to fabricate high-rate and cycling-stable hierarchical sphered cathode Li(1.2)Ni(0.13)Mn(0.54)Co(0.13)O2, by using an ionic interfusion method. The sphere-shaped hierarchical cathode is assembled with primary nanoplates with enhanced growth of nanocrystal planes in favor of Li(+) intercalation/deintercalation, such as (010), (100), and (110) planes. This material with such unique structural features exhibits outstanding rate capability, cyclability, and high discharge capacities, achieving around 70% (175 mAh g(-1)) of the capacity at 0.1 C rate within about 2.1 min of ultrafast charging. Such cathode is feasible to construct high-energy and high-power Li-ion batteries.

Novel hierarchical tantalum oxide-PDMS hybrid coating for medical implants: One pot synthesis, characterization and modulation of fibroblast proliferation.

PubMed

Tran, Phong A; Fox, Kate; Tran, Nhiem

2017-01-01

Surface properties such as morphology, roughness and charge density have a strong influence on the interaction of biomaterials and cells. Hierarchical materials with a combination of micron/submicron and nanoscale features for coating of medical implants could therefore have significant potential to modulate cellular responses and eventually improve the performance of the implants. In this study, we report a simple, one pot wet chemistry preparation of a hybrid coating system with hierarchical surface structures consisting of polydimethylsiloxane (PDMS) and tantalum oxide. Medical grade, amine functional PDMS was mixed with tantalum ethoxide which subsequently formed Ta 2 O 5 in situ through hydrolysis and condensation during coating process. The coatings were characterized by SEM, EDS, XPS, confocal scanning microscopy, contact angle measurement and in vitro cell culture. Varying PDMS and tantalum ethoxide ratios resulted in coatings of different surface textures ranging from smooth to submicro- and nano-structured. Strikingly, hierarchical surfaces containing both microscale (1-1.5μm) and nanoscale (86-163nm) particles were found on coatings synthesized with 20% and 40% (v/v) tantalum ethoxide. The coatings were similar in term of hydrophobicity but showed different surface roughness and chemical composition. Importantly, higher cell proliferation was observed on hybrid surface with hierarchical structures compared to pure PDMS or pure tantalum oxide. The coating process is simple, versatile, carried out under ambient condition and requires no special equipment. Copyright © 2016 Elsevier Inc. All rights reserved.

Genetically encoded lipid-polypeptide hybrid biomaterials that exhibit temperature-triggered hierarchical self-assembly

NASA Astrophysics Data System (ADS)

Mozhdehi, Davoud; Luginbuhl, Kelli M.; Simon, Joseph R.; Dzuricky, Michael; Berger, Rüdiger; Varol, H. Samet; Huang, Fred C.; Buehne, Kristen L.; Mayne, Nicholas R.; Weitzhandler, Isaac; Bonn, Mischa; Parekh, Sapun H.; Chilkoti, Ashutosh

2018-05-01

Post-translational modification of proteins is a strategy widely used in biological systems. It expands the diversity of the proteome and allows for tailoring of both the function and localization of proteins within cells as well as the material properties of structural proteins and matrices. Despite their ubiquity in biology, with a few exceptions, the potential of post-translational modifications in biomaterials synthesis has remained largely untapped. As a proof of concept to demonstrate the feasibility of creating a genetically encoded biohybrid material through post-translational modification, we report here the generation of a family of three stimulus-responsive hybrid materials—fatty-acid-modified elastin-like polypeptides—using a one-pot recombinant expression and post-translational lipidation methodology. These hybrid biomaterials contain an amphiphilic domain, composed of a β-sheet-forming peptide that is post-translationally functionalized with a C14 alkyl chain, fused to a thermally responsive elastin-like polypeptide. They exhibit temperature-triggered hierarchical self-assembly across multiple length scales with varied structure and material properties that can be controlled at the sequence level.

Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitors and Redox Electrolyte Energy Storage.

PubMed

Jayaramulu, Kolleboyina; Dubal, Deepak P; Nagar, Bhawna; Ranc, Vaclav; Tomanec, Ondrej; Petr, Martin; Datta, Kasibhatta Kumara Ramanatha; Zboril, Radek; Gómez-Romero, Pedro; Fischer, Roland A

2018-04-01

The design of advanced high-energy-density supercapacitors requires the design of unique materials that combine hierarchical nanoporous structures with high surface area to facilitate ion transport and excellent electrolyte permeability. Here, shape-controlled 2D nanoporous carbon sheets (NPSs) with graphitic wall structure through the pyrolysis of metal-organic frameworks (MOFs) are developed. As a proof-of-concept application, the obtained NPSs are used as the electrode material for a supercapacitor. The carbon-sheet-based symmetric cell shows an ultrahigh Brunauer-Emmett-Teller (BET)-area-normalized capacitance of 21.4 µF cm -2 (233 F g -1 ), exceeding other carbon-based supercapacitors. The addition of potassium iodide as redox-active species in a sulfuric acid (supporting electrolyte) leads to the ground-breaking enhancement in the energy density up to 90 Wh kg -1 , which is higher than commercial aqueous rechargeable batteries, maintaining its superior power density. Thus, the new material provides a double profits strategy such as battery-level energy and capacitor-level power density. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

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

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr; Poienar, Maria; Guesdon, Anne

Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containingmore » phosphonates organic building units crystallizing in different structural types. - Graphical abstract: Phosphate dendrite like and phosphonate platelet crystals.« less

Squid pen-inspired chitinous functional materials: Hierarchical chitin fibers by centrifugal jet-spinning and transparent chitin fiber-reinforced composite

NASA Astrophysics Data System (ADS)

Jeong, Seung-Hwan; Kim, Joong-Kwon; Lim, Young-Woo; Hwang, Hyun-Bin; Kwon, Hee-Young; Bae, Byeong-Soo; Jin, Jungho

2018-01-01

Here, inspired by the fibrous composite structure of a squid pen, we introduce hierarchical chitin fibers (herein, termed "Chiber") and their transparent composites and demonstrate the potential of these chitinous functional materials as a sustainable separation-membrane and reinforcing filler for composites. We employ a centrifugal jet-spinning process to fabricate Chiber with aligned chitin nanofibrillar architectures, for which we discuss the processing-morphology relationship. A nonwoven fiber-mat made of Chiber exhibits excellent adsorbing performance for a toxic ionic dye (Congo Red), and has a low coefficient of thermal expansion comparable to that of glass fibers. Finally, we demonstrate a squid pen-mimetic transparent composite using Chiber and investigate its optical property.

Colloidal quantum dot solar cells exploiting hierarchical structuring.

PubMed

Labelle, André J; Thon, Susanna M; Masala, Silvia; Adachi, Michael M; Dong, Haopeng; Farahani, Maryam; Ip, Alexander H; Fratalocchi, Andrea; Sargent, Edward H

2015-02-11

Extremely thin-absorber solar cells offer low materials utilization and simplified manufacture but require improved means to enhance photon absorption in the active layer. Here, we report enhanced-absorption colloidal quantum dot (CQD) solar cells that feature transfer-stamped solution-processed pyramid-shaped electrodes employed in a hierarchically structured device. The pyramids increase, by up to a factor of 2, the external quantum efficiency of the device at absorption-limited wavelengths near the absorber band edge. We show that absorption enhancement can be optimized with increased pyramid angle with an appreciable net improvement in power conversion efficiency, that is, with the gain in current associated with improved absorption and extraction overcoming the smaller fractional decrease in open-circuit voltage associated with increased junction area. We show that the hierarchical combination of micron-scale structured electrodes with nanoscale films provides for an optimized enhancement at absorption-limited wavelengths. We fabricate 54.7° pyramid-patterned electrodes, conformally apply the quantum dot films, and report pyramid CQD solar cells that exhibit a 24% improvement in overall short-circuit current density with champion devices providing a power conversion efficiency of 9.2%.

3D Networked Tin Oxide/Graphene Aerogel with a Hierarchically Porous Architecture for High-Rate Performance Sodium-Ion Batteries.

PubMed

Xie, Xiuqiang; Chen, Shuangqiang; Sun, Bing; Wang, Chengyin; Wang, Guoxiu

2015-09-07

Low-cost and sustainable sodium-ion batteries are regarded as a promising technology for large-scale energy storage and conversion. The development of high-rate anode materials is highly desirable for sodium-ion batteries. The optimization of mass transport and electron transfer is crucial in the discovery of electrode materials with good high-rate performances. Herein, we report the synthesis of 3 D interconnected SnO2 /graphene aerogels with a hierarchically porous structure as anode materials for sodium-ion batteries. The unique 3 D architecture was prepared by a facile in situ process, during which cross-linked 3 D conductive graphene networks with macro-/meso-sized hierarchical pores were formed and SnO2 nanoparticles were dispersed uniformly on the graphene surface simultaneously. Such a 3 D functional architecture not only facilitates the electrode-electrolyte interaction but also provides an efficient electron pathway within the graphene networks. When applied as anode materials in sodium-ion batteries, the as-prepared SnO2 /graphene aerogel exhibited high reversible capacity, improved cycling performance compared to SnO2 , and promising high-rate capability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Setting Directions: Anisotropy in Hierarchically Organized Porous Silica

PubMed Central

2017-01-01

Structural hierarchy, porosity, and isotropy/anisotropy are highly relevant factors for mechanical properties and thereby the functionality of porous materials. However, even though anisotropic and hierarchically organized, porous materials are well known in nature, such as bone or wood, producing the synthetic counterparts in the laboratory is difficult. We report for the first time a straightforward combination of sol–gel processing and shear-induced alignment to create hierarchical silica monoliths exhibiting anisotropy on the levels of both, meso- and macropores. The resulting material consists of an anisotropic macroporous network of struts comprising 2D hexagonally organized cylindrical mesopores. While the anisotropy of the mesopores is an inherent feature of the pores formed by liquid crystal templating, the anisotropy of the macropores is induced by shearing of the network. Scanning electron microscopy and small-angle X-ray scattering show that the majority of network forming struts is oriented towards the shearing direction; a quantitative analysis of scattering data confirms that roughly 40% of the strut volume exhibits a preferred orientation. The anisotropy of the material’s macroporosity is also reflected in its mechanical properties; i.e., the Young’s modulus differs by nearly a factor of 2 between the directions of shear application and perpendicular to it. Unexpectedly, the adsorption-induced strain of the material exhibits little to no anisotropy. PMID:28989232

Hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 hollow spherical as cathode material for Li-ion battery

NASA Astrophysics Data System (ADS)

Zhang, Yu; Zhu, Tianjiao; Lin, Liu; Yuan, Mengwei; Li, Huifeng; Sun, Genban; Ma, Shulan

2017-11-01

Lithium-rich manganese-based layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, a great loss of irreversible capacity at the initial cycle, poor cycle stability, and rate performance severely restrict its application. Herein, we develop a new strategy to synthesize hierarchical hollow Li1.2Mn0.54Ni0.13Co0.13O2 microspheres using sucrose and cetyltrimethylammonium bromide as a soft template combined with hydrothermal assisted homogeneous precipitation method. The hollow microspheres are assembled by the primary particles with the size of 50 nm. As a result, the as-prepared material exhibits high reversible capacity, good cycling stability, and excellent rate property. It delivers a high initial discharge capacity of 305.9 mAh g-1 at 28 mA g-1 with coulombic efficiency of 80%. Even at high current density of 560 mA g-1, the sample also shows a stable discharge capacity of 215 mAh g-1. The enhanced electrochemical properties are attributed to the stable hierarchical hollow sphere structure and the appropriate contact area between electrode and electrolyte, thus effectively improve the lithium-ion intercalation and deintercalation kinetics. [Figure not available: see fulltext.

Hierarchical structured Sm2O3 modified CuO nanoflowers as electrode materials for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, Xiaojuan; He, Mingqian; He, Ping; Liu, Hongtao; Bai, Hongmei; Chen, Jingchao; He, Shaoying; Zhang, Xingquan; Dong, Faqing; Chen, Yang

2017-12-01

By a simple and cost effective chemical precipitation-hydrothermal method, novel hierarchical structured Sm2O3 modified CuO nanoflowers are prepared and investigated as electrode materials for supercapacitors. The physical properties of prepared materials are characterized by XRD, FE-SEM, EDX and FTIR techniques. Furthermore, electrochemical performances of prepared materials are investigated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectrum in 1.0 M KOH electrolyte. The resulting Sm2O3 modified CuO based electrodes exhibit obviously enhanced capacitive properties owing to the unique nanostructures and strong synergistic effects. It is worth noting that the optimized SC-3 based electrode exhibits the best electrochemical performances in all prepared electrodes, including higher specific capacitance (383.4 F g-1 at 0.5 A g-1) and good rate capability (393.2 F g-1 and 246.3 F g-1 at 0.3 A g-1 and 3.0 A g-1, respectively), as well as excellent cycling stability (84.6% capacitance retention after 2000 cycles at 1.0 A g-1). The present results show that Sm2O3 is used as a promising modifier to change the morphology and improve electrochemical performances of CuO materials.

Kelp-derived three-dimensional hierarchical porous N, O-doped carbon for flexible solid-state symmetrical supercapacitors with excellent performance

NASA Astrophysics Data System (ADS)

Zhang, Yifu; Jiang, Hanmei; Wang, Qiushi; Zheng, Jiqi; Meng, Changgong

2018-07-01

Three-dimensional (3D) porous N, O-doped carbon with hierarchical structures composed of micropores, mesopores and macropores were synthesized by the direct carbonization of kelp with a "self-activation" process. The as-obtained 3D N, O-doped carbon remained abundant N and O functional groups and the BET specific surface area measured 656 m2 g-1. 3D hierarchical porous structures with the pore size ranged from several nanometers to hundred nanometers and lots of pores were attributed to mesopores with the average pore size of about 5.4 nm. Electrochemical properties of the 3D hierarchical porous N, O-doped carbon as a supercapactior (SC) electrode were investigated and it delivered excellent capacitance of 669 mF cm-2 at 1 mA cm-2 due to its 3D hierarchical porous structures with high specific surface area which is beneficial for improving ionic storage and transportation in electrodes. This kelp-derived carbon exhibited excellent cyclic performance with the retention of 104% after 10,000 cycles. A flexible solid-state symmetric SC (SSC) device was fabricated using the 3D hierarchical porous N, O-doped carbon and delivered an excellent capacitance of 412 mF cm-2 at 2 mA cm-2 and satisfying cyclic stability with the retention of 85% after 10,000 cycles. The areal energy density of the SSC device reach up to 0.146 mWh cm-2 at the power density of 0.8 mW cm-2. This facile route for low-cost carbonaceous materials with novel architecture and functionality can be as a promising alternative to synthesize biomass carbon for practical SC application.

TEOA-mediated formation of hollow core-shell structured CoNi2S4 nanospheres as a high-performance electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Liang, Jun; Li, Meng; Chai, Yao; Luo, Min; Li, Li

2017-09-01

In this study, we report for the first time a cost-effective and general approach for the high-yield synthesis of a hierarchical core-shell and hollow structure of ternary CoNi2S4 in a triethanolamine (TEOA)-assisted hydrothermal system. It is found that a continuous increase in TEOA usages facilitates the formation and transformation of hierarchical CoNi2S4 hollow nanospheres, and the formation mechanism of the unique structure is revealed to be assembly-then-inside-out evacuation and Ostwald ripening mechanism during the sulfidation process. More importantly, when used as faradaic electrode for supercapacitors, the hierarchical hollow CoNi2S4 nanospheres display not only exceptional pseudocapacitve performance with high specific capacitance (2035 Fg-1 at 1 Ag-1) and excellent rate capability (1215 Fg-1 at 20 Ag-1), but also superior cycling stability, with only about 8.7% loss over 3000 cycles at 10 Ag-1. This work can provide some guidance for us in the structural and compositional tuning of mixed binary-metal sulfides toward many desired applications.

Three-dimensional carbon architectures for electrochemical capacitors.

PubMed

Song, Yu; Liu, Tianyu; Qian, Fang; Zhu, Cheng; Yao, Bin; Duoss, Eric; Spadaccini, Christopher; Worsley, Marcus; Li, Yat

2018-01-01

Three-dimensional (3D) carbon-based materials are emerging as promising electrode candidates for energy storage devices. In comparison to the 1D and 2D structures, 3D morphology offers new opportunities in rational design and synthesis of novel architectures tailor-made for promoting electrochemical performance. The capability of building hierarchical porous structures with 3D configuration can significantly advance the performance of energy storage devices by simultaneously enhancing the ion-accessible surface area and ion diffusion. This feature article presents an overview of recent progress in design, synthesis and implementation of 3D carbon-based materials as electrodes for electrochemical capacitors. Synthesis methodologies of four types of 3D carbon-based electrodes: 3D exfoliated carbon structures, 3D graphene scaffolds, 3D hierarchical porous carbon foams, as well as 3D architectures with periodic pores derived from direct ink writing, are thoroughly discussed and highlighted with selected experimental works. Finally, key opportunities and challenges in which different 3D carbons can significantly impact the energy storage and conversion communities will be provided. Copyright © 2017 Elsevier Inc. All rights reserved.

Controllable synthesis of CuS hollow microflowers hierarchical structures for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Yanxia; Zhou, Zhaoxiao; Zhang, Shengping; Luo, Wenhao; Zhang, Guofeng

2018-06-01

One of the major challenges of high-performance asymmetric supercapacitors is engineering electrode materials with high capacitance and good cycling stability. Hence, we have successfully prepared different CuS hierarchical structures including CuS tubular structures (T-CuS), CuS hollow microspheres (S-CuS) and CuS hollow microflowers (H-CuS) by adjusting the solvents, all of which are investigated as electrode materials for supercapacitors. Among them, the H-CuS electrode exhibits the best electrochemical performance involving a high capacitance of 536.7 F g-1 at a current density of 8 A g-1 and excellent cycling stability with 83.6% capacitance retention for 20,000 continuous cycles at a current density of 5 A g-1. In addition, an asymmetric supercapacitor has assembled with H-CuS as positive electrode and activated carbon (AC) as negative electrode, which exhibits a desirable energy density of 15.97 W h kg-1 when the power density is 185.4 W kg-1. These desirable electrochemical performances powerfully demonstrate that the H-CuS electrode has promising potential for applications in energy storage fields.

Supramolecular "Step Polymerization" of Preassembled Micelles: A Study of "Polymerization" Kinetics.

PubMed

Yang, Chaoying; Ma, Xiaodong; Lin, Jiaping; Wang, Liquan; Lu, Yingqing; Zhang, Liangshun; Cai, Chunhua; Gao, Liang

2018-03-01

In nature, sophisticated functional materials are created through hierarchical self-assembly of nanoscale motifs, which has inspired the fabrication of man-made materials with complex architectures for a variety of applications. Herein, a kinetic study on the self-assembly of spindle-like micelles preassembled from polypeptide graft copolymers is reported. The addition of dimethylformamide and, subsequently, a selective solvent (water) can generate a "reactive point" at both ends of the spindles as a result of the existence of structural defects, which induces the "polymerization" of the spindles into nanowires. Experimental results combined with dissipative particle dynamics simulations show that the polymerization of the micellar subunits follows a step-growth polymerization mechanism with a second-order reaction characteristic. The assembly rate of the micelles is dependent on the subunit concentration and on the activity of the reactive points. The present work reveals a law governing the self-assembly kinetics of micelles with structural defects and opens the door for the construction of hierarchical structures with a controllable size through supramolecular step polymerization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Stretchable Superhydrophobic Composite Coating Based on Self-Adaptive Deformation of Hierarchical Structures.

PubMed

Hu, Xin; Tang, Changyu; He, Zhoukun; Shao, Hong; Xu, Keqin; Mei, Jun; Lau, Woon-Ming

2017-05-01

With the rapid development of stretchable electronics, functional textiles, and flexible sensors, water-proof protection materials are required to be built on various highly flexible substrates. However, maintaining the antiwetting of superhydrophobic surface under stretching is still a big challenge since the hierarchical structures at hybridized micro-nanoscales are easily damaged following large deformation of the substrates. This study reports a highly stretchable and mechanically stable superhydrophobic surface prepared by a facile spray coating of carbon black/polybutadiene elastomeric composite on a rubber substrate followed by thermal curing. The resulting composite coating can maintain its superhydrophobic property (water contact angle ≈170° and sliding angle <4°) at an extremely large stretching strain of up to 1000% and can withstand 1000 stretching-releasing cycles without losing its superhydrophobic property. Furthermore, the experimental observation and modeling analysis reveal that the stable superhydrophobic properties of the composite coating are attributed to the unique self-adaptive deformation ability of 3D hierarchical roughness of the composite coating, which delays the Cassie-Wenzel transition of surface wetting. In addition, it is first observed that the damaged coating can automatically recover its superhydrophobicity via a simple stretching treatment without incorporating additional hydrophobic materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical templating in deposition of semi-covalently imprinted inverse opal polythiophene film for femtomolar determination of human serum albumin.

PubMed

Dabrowski, Marcin; Cieplak, Maciej; Sharma, Piyush Sindhu; Borowicz, Pawel; Noworyta, Krzysztof; Lisowski, Wojciech; D'Souza, Francis; Kuhn, Alexander; Kutner, Wlodzimierz

2017-08-15

Nanostructured artificial receptor materials with unprecedented hierarchical structure for determination of human serum albumin (HSA) are designed and fabricated. For that purpose a new hierarchical template is prepared. This template allowed for simultaneous structural control of the deposited molecularly imprinted polymer (MIP) film on three length scales. A colloidal crystal templating with optimized electrochemical polymerization of 2,3'-bithiophene enables deposition of an MIP film in the form of an inverse opal. Thickness of the deposited polymer film is precisely controlled with the number of current oscillations during potentiostatic deposition of the imprinted poly(2,3'-bithiophene) film. Prior immobilization of HSA on the colloidal crystal allows formation of molecularly imprinted cavities exclusively on the internal surface of the pores. Furthermore, all binding sites are located on the surface of the imprinted cavities at locations corresponding to positions of functional groups present on the surface of HSA molecules due to prior derivatization of HSA molecules with appropriate functional monomers. This synergistic strategy results in a material with superior recognition performance. Integration of the MIP film as a recognition unit with a sensitive extended-gate field-effect transistor (EG-FET) transducer leads to highly selective HSA determination in the femtomolar concentration range. Copyright © 2017 Elsevier B.V. All rights reserved.

Hierarchical ferroelectric and ferrotoroidic polarizations coexistent in nano-metamaterials

PubMed Central

Shimada, Takahiro; Lich, Le Van; Nagano, Koyo; Wang, Jie; Kitamura, Takayuki

2015-01-01

Tailoring materials to obtain unique, or significantly enhanced material properties through rationally designed structures rather than chemical constituents is principle of metamaterial concept, which leads to the realization of remarkable optical and mechanical properties. Inspired by the recent progress in electromagnetic and mechanical metamaterials, here we introduce the concept of ferroelectric nano-metamaterials, and demonstrate through an experiment in silico with hierarchical nanostructures of ferroelectrics using sophisticated real-space phase-field techniques. This new concept enables variety of unusual and complex yet controllable domain patterns to be achieved, where the coexistence between hierarchical ferroelectric and ferrotoroidic polarizations establishes a new benchmark for exploration of complexity in spontaneous polarization ordering. The concept opens a novel route to effectively tailor domain configurations through the control of internal structure, facilitating access to stabilization and control of complex domain patterns that provide high potential for novel functionalities. A key design parameter to achieve such complex patterns is explored based on the parity of junctions that connect constituent nanostructures. We further highlight the variety of additional functionalities that are potentially obtained from ferroelectric nano-metamaterials, and provide promising perspectives for novel multifunctional devices. This study proposes an entirely new discipline of ferroelectric nano-metamaterials, further driving advances in metamaterials research. PMID:26424484

Biomass derived nitrogen-doped hierarchical porous carbon sheets for supercapacitors with high performance.

PubMed

Wang, Cunjing; Wu, Dapeng; Wang, Hongju; Gao, Zhiyong; Xu, Fang; Jiang, Kai

2018-08-01

A facile potassium chloride salt-locking technique combined with hydrothermal treatment on precursors was explored to prepare nitrogen-doped hierarchical porous carbon sheets in air from biomass. Benefiting from the effective synthesis strategy, the as-obtained carbon possesses a unique nitrogen-doped thin carbon sheet structure with abundant hierarchical pores and large specific surface areas of 1459 m 2  g -1 . The doped nitrogen in carbon framework has a positive effect on the electrochemical properties of the electrode material, the thin carbon sheet structure benefits for fast ion transfer, the abundant meso-pores provide convenient channels for rapid charge transportation, large specific surface area and lots of micro-pores guarantee sufficient ion-storage sites. Therefore, applied for supercapacitors, the carbon electrode material exhibits an outstanding specific capacitance of 451 F g -1 at 0.5 A g -1 in a three-electrode system. Moreover, the assembled symmetric supercapacitor based on two identical carbon electrodes also displays high specific capacitance of 309 F g -1 at 0.5 A g -1 , excellent rate capacity and remarkable cycling stability with 99.3% of the initial capacitance retention after 10,000 cycles at 5 A -1 . The synthesis strategy avoids expensive inert gas protection and the use of corrosive KOH and toxic ZnCl 2 activated reagents, representing a promising green route to design advanced carbon electrode materials from biomass for high-capacity supercapacitors. Copyright © 2018. Published by Elsevier Inc.

Soybean Root-Derived Hierarchical Porous Carbon as Electrode Material for High-Performance Supercapacitors in Ionic Liquids.

PubMed

Guo, Nannan; Li, Min; Wang, Yong; Sun, Xingkai; Wang, Feng; Yang, Ru

2016-12-14

Soybeans are extensively cultivated worldwide as human food. However, large quantities of soybean roots (SRs), which possess an abundant three-dimensional (3D) structure, remain unused and produce enormous pressure on the environment. Here, 3D hierarchical porous carbon was prepared by the facile carbonization of SRs followed by chemical activation. The as-prepared material, possessing large specific surface area (2143 m 2 g -1 ), good electrical conductivity, and unique 3D hierarchical porosity, shows outstanding electrochemical performance as an electrode material for supercapacitors, such as a high capacitance (276 F g -1 at 0.5 A g -1 ), superior cycle stability (98% capacitance retention after 10,000 cycles at 5 A g -1 ), and good rate capability in a symmetric two-electrode supercapacitor in 6 M KOH. Furthermore, the maximum energy density of as-assembled symmetric supercapacitor can reach 100.5 Wh kg -1 in neat EMIM BF 4 . Moreover, a value of 40.7 Wh kg -1 is maintained at ultrahigh power density (63000 W kg -1 ). These results show that the as-assembled supercapacitor can simultaneously deliver superior energy and power density.

Hierarchically Patterned Noncovalent Functionalization of 2D Materials by Controlled Langmuir-Schaefer Conversion.

PubMed

Davis, Tyson C; Bang, Jae Jin; Brooks, Jacob T; McMillan, David G; Claridge, Shelley A

2018-01-30

Noncovalent monolayer chemistries are often used to functionalize 2D materials. Nanoscopic ligand ordering has been widely demonstrated (e.g., lying-down lamellar phases of functional alkanes); however, combining this control with micro- and macroscopic patterning for practical applications remains a significant challenge. A few reports have demonstrated that standing phase Langmuir films on water can be converted into nanoscopic lying-down molecular domains on 2D substrates (e.g., graphite), using horizontal dipping (Langmuir-Schaefer, LS, transfer). Molecular patterns are known to form at scales up to millimeters in Langmuir films, suggesting the possibility of transforming such structures into functional patterns on 2D materials. However, to our knowledge, this approach has not been investigated, and the rules governing LS conversion are not well understood. In part, this is because the conversion process is mechanistically very different from classic LS transfer of standing phases; challenges also arise due to the need to characterize structure in noncovalently adsorbed ligand layers <0.5 nm thick, at scales ranging from millimeters to nanometers. Here, we show that scanning electron microscopy enables diynoic acid lying-down phases to be imaged across this range of scales; using this structural information, we establish conditions for LS conversion to create hierarchical microscopic and nanoscopic functional patterns. Such control opens the door to tailoring noncovalent surface chemistry of 2D materials to pattern local interactions with the environment.

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

Fu, Fang; Yao, Yuze; Wang, Haiyan

Rational and precise control of the structure and dimension of electrode materials is an efficient way to improve their electrochemical performance. In this work, solvothermal or co-precipitation method is used to synthesize lithium-rich layered oxide materials of Li1.2Mn0.56Co0.12Ni0.12O2 (LLO) with various morphologies and structures, including microspheres, microrods, nanoplates, and irregular nanoparticles. These materials exhibit strong structure- dependent electrochemical properties. The porous hierarchical structured LLO microrods exhibit the best performance, delivering a discharge capacity of 264.6 mAh g(-1) at 0.5 C with over 91% retention after 100 cycles. At a high rate of 5 C, a high discharge capacity of 173.6more » mAh g(-1) can be achieved. This work reveals the relationship between the morphologies and electrochemical properties of LLO cathode materials, and provides a feasible approach to fabricating robust and high-performance electrode materials for lithium-ion batteries.« less

3D flower-like hierarchical Ag@nickel-cobalt hydroxide microsphere with enhanced electrochemical properties

NASA Astrophysics Data System (ADS)

Lv, Zijian; Zhong, Qin; Bu, Yunfei; Wu, Junpeng

2016-10-01

The morphology and electrical conductivity are essential to electrochemical performance of electrode materials in renewable energy conversion and storage technologies such as fuel cells and supercapacitors. Here, we explored a facile method to grow Ag@nickel-cobalt layered double hydroxide (Ag@Ni/Co-LDHs) with 3D flower-like microsphere structure. The results show the morphology of Ni/Co-LDHs varies with the introduction of Ag species. The prepared Ag@Ni/Co-LDHs not only exhibits an open hierarchical structure with high specific capacitance but also shows good electrical conductivity to support fast electron transport. Benefiting from the unique structural features, these flower-like Ag@Ni/Co-LDHs microspheres have impressive specific capacitance as high as 1768 F g-1 at 1 A g-1. It can be concluded that engineering the structure of the electrode can increase the efficiency of the specific capacitance as a battery-type electrode for hybrid supercapacitors.

Quantitative nanoscopy: Tackling sampling limitations in (S)TEM imaging of polymers and composites.

PubMed

Gnanasekaran, Karthikeyan; Snel, Roderick; de With, Gijsbertus; Friedrich, Heiner

2016-01-01

Sampling limitations in electron microscopy questions whether the analysis of a bulk material is representative, especially while analyzing hierarchical morphologies that extend over multiple length scales. We tackled this problem by automatically acquiring a large series of partially overlapping (S)TEM images with sufficient resolution, subsequently stitched together to generate a large-area map using an in-house developed acquisition toolbox (TU/e Acquisition ToolBox) and stitching module (TU/e Stitcher). In addition, we show that quantitative image analysis of the large scale maps provides representative information that can be related to the synthesis and process conditions of hierarchical materials, which moves electron microscopy analysis towards becoming a bulk characterization tool. We demonstrate the power of such an analysis by examining two different multi-phase materials that are structured over multiple length scales. Copyright © 2015 Elsevier B.V. All rights reserved.

Hierarchically Structured Electrospun Fibers

DTIC Science & Technology

2013-01-07

polymeric materials such as ceramics and metals, can be fabricated into nanofibers via electrospinning . An assortment of natural polymers, such as the...are traditionally made by electrospinning of the core material, which serves as a template for the deposition of the shell layer via chemical vapor...been made from the contraction of a manganese oxide sol gel upon solvent evaporation, as well as from zinc oxide and silicon dioxide using vapor

Hierarchical mutual information for the comparison of hierarchical community structures in complex networks

NASA Astrophysics Data System (ADS)

Perotti, Juan Ignacio; Tessone, Claudio Juan; Caldarelli, Guido

2015-12-01

The quest for a quantitative characterization of community and modular structure of complex networks produced a variety of methods and algorithms to classify different networks. However, it is not clear if such methods provide consistent, robust, and meaningful results when considering hierarchies as a whole. Part of the problem is the lack of a similarity measure for the comparison of hierarchical community structures. In this work we give a contribution by introducing the hierarchical mutual information, which is a generalization of the traditional mutual information and makes it possible to compare hierarchical partitions and hierarchical community structures. The normalized version of the hierarchical mutual information should behave analogously to the traditional normalized mutual information. Here the correct behavior of the hierarchical mutual information is corroborated on an extensive battery of numerical experiments. The experiments are performed on artificial hierarchies and on the hierarchical community structure of artificial and empirical networks. Furthermore, the experiments illustrate some of the practical applications of the hierarchical mutual information, namely the comparison of different community detection methods and the study of the consistency, robustness, and temporal evolution of the hierarchical modular structure of networks.

Biomass-derived nitrogen-doped porous carbons with tailored hierarchical porosity and high specific surface area for high energy and power density supercapacitors

NASA Astrophysics Data System (ADS)

Sun, Junting; Niu, Jin; Liu, Mengyue; Ji, Jing; Dou, Meiling; Wang, Feng

2018-01-01

Porous carbon materials with hierarchical structures attract intense interest for the development of high-performance supercapacitors. Herein, we demonstrate a facile and efficient strategy to synthesize nitrogen-doped hierarchically porous carbons with tailored porous structure combined with high specific surface area (SSA), which involves a pre-carbonization and a subsequent carbonization combined with KOH activation of silkworm cocoon precursors. Through adjusting the mass ratio of the activator (KOH) to pre-carbonized precursor in the activation process, the hierarchically porous carbon prepared at the mass ratio of 2 (referred to as NHPC-2) possesses a high defect density and a high SSA of 3386 m2 g-1 as well as the relatively high volumetric proportion of mesopores and macropores (45.5%). As a result, the energy density and power density of the symmetric supercapacitor based on NHPC-2 electrode are as high as 34.41 Wh kg-1 and 31.25 kW kg-1 in organic-solvent electrolyte, and are further improved to 112.1 Wh kg-1 and 23.91 kW kg-1 in ionic-liquid electrolyte.

Construction of three-dimensional graphene interfaces into carbon fiber textiles for increasing deposition of nickel nanoparticles: flexible hierarchical magnetic textile composites for strong electromagnetic shielding

NASA Astrophysics Data System (ADS)

Bian, Xing-Ming; Liu, Lin; Li, Hai-Bing; Wang, Chan-Yuan; Xie, Qing; Zhao, Quan-Liang; Bi, Song; Hou, Zhi-Ling

2017-01-01

Since manipulating electromagnetic waves with electromagnetic active materials for environmental and electric engineering is a significant task, here a novel prototype is reported by introducing reduced graphene oxide (RGO) interfaces in carbon fiber (CF) networks for a hierarchical carbon fiber/reduced graphene oxide/nickel (CF-RGO-Ni) composite textile. Upon charaterizations of the microscopic morphologies, electrical and magnetic properties, the presence of three-dimensional RGO interfaces and bifunctional nickel nanoparticles substantially influences the related physical properties in the resulting hierarchical composite textiles. Eletromagnetic interference (EMI) shielding performance suggests that the hierarchical composite textiles hold a strong shielding effectiveness greater than 61 dB, showing greater advantages than conventional polymeric and foamy shielding composites. As a polymer-free lightweight structure, flexible CF-RGO-Ni composites of all electromagnetic active components offer unique understanding of the multi-scale and multiple mechanisms in electromagnetic energy consumption. Such a novel prototype of shielding structures along with convenient technology highlight a strategy to achieve high-performance EMI shielding, coupled with a universal approach for preparing advanced lightweight composites with graphene interfaces.

Biomimetic fabrication of a three-level hierarchical calcium phosphate/collagen/hydroxyapatite scaffold for bone tissue engineering.

PubMed

Zhou, Changchun; Ye, Xingjiang; Fan, Yujiang; Ma, Liang; Tan, Yanfei; Qing, Fangzu; Zhang, Xingdong

2014-09-01

A three-level hierarchical calcium phosphate/collagen/hydroxyapatite (CaP/Col/HAp) scaffold for bone tissue engineering was developed using biomimetic synthesis. Porous CaP ceramics were first prepared as substrate materials to mimic the porous bone structure. A second-level Col network was then composited into porous CaP ceramics by vacuum infusion. Finally, a third-level HAp layer was achieved by biomimetic mineralization. The three-level hierarchical biomimetic scaffold was characterized using scanning electron microscopy, energy-dispersive x-ray spectra, x-ray diffraction and Fourier transform infrared spectroscopy, and the mechanical properties of the scaffold were evaluated using dynamic mechanical analysis. The results show that this scaffold exhibits a similar structure and composition to natural bone tissues. Furthermore, this three-level hierarchical biomimetic scaffold showed enhanced mechanical strength compared with pure porous CaP scaffolds. The biocompatibility and osteoinductivity of the biomimetic scaffolds were evaluated using in vitro and in vivo tests. Cell culture results indicated the good biocompatibility of this biomimetic scaffold. Faster and increased bone formation was observed in these scaffolds following a six-month implantation in the dorsal muscles of rabbits, indicating that this biomimetic scaffold exhibits better osteoinductivity than common CaP scaffolds.

Construction of three-dimensional graphene interfaces into carbon fiber textiles for increasing deposition of nickel nanoparticles: flexible hierarchical magnetic textile composites for strong electromagnetic shielding.

PubMed

Bian, Xing-Ming; Liu, Lin; Li, Hai-Bing; Wang, Chan-Yuan; Xie, Qing; Zhao, Quan-Liang; Bi, Song; Hou, Zhi-Ling

2017-01-27

Since manipulating electromagnetic waves with electromagnetic active materials for environmental and electric engineering is a significant task, here a novel prototype is reported by introducing reduced graphene oxide (RGO) interfaces in carbon fiber (CF) networks for a hierarchical carbon fiber/reduced graphene oxide/nickel (CF-RGO-Ni) composite textile. Upon charaterizations of the microscopic morphologies, electrical and magnetic properties, the presence of three-dimensional RGO interfaces and bifunctional nickel nanoparticles substantially influences the related physical properties in the resulting hierarchical composite textiles. Eletromagnetic interference (EMI) shielding performance suggests that the hierarchical composite textiles hold a strong shielding effectiveness greater than 61 dB, showing greater advantages than conventional polymeric and foamy shielding composites. As a polymer-free lightweight structure, flexible CF-RGO-Ni composites of all electromagnetic active components offer unique understanding of the multi-scale and multiple mechanisms in electromagnetic energy consumption. Such a novel prototype of shielding structures along with convenient technology highlight a strategy to achieve high-performance EMI shielding, coupled with a universal approach for preparing advanced lightweight composites with graphene interfaces.

Self-assembled three-dimensional hierarchical graphene/polypyrrole nanotube hybrid aerogel and its application for supercapacitors.

PubMed

Ye, Shibing; Feng, Jiachun

2014-06-25

A three-dimensional hierarchical graphene/polypyrrole aerogel (GPA) has been fabricated using graphene oxide (GO) and already synthesized one-dimensional hollow polypyrrole nanotubes (PNTs) as the feedstock. The amphiphilic GO is helpful in effectively promoting the dispersion of well-defined PNTs to result in a stable, homogeneous GO/PNT complex solution, while the PNTs not only provide a large accessible surface area for fast transport of hydrate ions but also act as spacers to prevent the restacking of graphene sheets. By a simple one-step reduction self-assembly process, hierarchically structured, low-density, highly compressible GPAs are easily obtained, which favorably combine the advantages of graphene and PNTs. The supercapacitor electrodes based on such materials exhibit excellent electrochemical performance, including a high specific capacitance up to 253 F g(-1), good rate performance, and outstanding cycle stability. Moreover, this method may be feasible to prepare other graphene-based hybrid aerogels with structure-controllable nanostructures in large scale, thereby holding enormous potential in many application fields.

Fabrication of hierarchical porous hollow carbon spheres with few-layer graphene framework and high electrochemical activity for supercapacitor

NASA Astrophysics Data System (ADS)

Chen, Jing; Hong, Min; Chen, Jiafu; Hu, Tianzhao; Xu, Qun

2018-06-01

Porous amorphous carbons with large number of defects and dangling bonds indicate great potential application in energy storage due to high specific surface area and strong adsorption properties, but poor conductivity and pore connection limit their practical application. Here few-layer graphene framework with high electrical conductivity is embedded and meanwhile hierarchical porous structure is constructed in amorphous hollow carbon spheres (HCSs) by catalysis of Fe clusters of angstrom scale, which are loaded in the interior of crosslinked polystyrene via a novel method. These unique HCSs effectively integrate the inherent properties from two-dimensional sp2-hybridized carbon, porous amorphous carbon, hierarchical pore structure and thin shell, leading to high specific capacitance up to 561 F g-1 at a current density of 0.5 A g-1 as an electrode of supercapacitor with excellent recyclability, which is much higher than those of other reported porous carbon materials up to present.

Palladium nanoparticles dispersed on the hollow aluminosilicate microsphere@hierarchical γ-AlOOH as an excellent catalyst for the hydrogenation of nitroarenes under ambient conditions

NASA Astrophysics Data System (ADS)

Tian, Meng; Cui, Xueliang; Dong, Chunxu; Dong, Zhengping

2016-12-01

In this study, a novel catalyst has been prepared through supporting Pd nanoparticles (NPs) on the surface of boehmite (γ-AlOOH) based hollow aluminosilicate microspheres (HAM@γ-AlOOH). The prepared Pd/HAM@γ-AlOOH catalyst has high catalytic activity for the hydrogenation of nitroarenes to their corresponding amino derivatives with high yields at ambient conditions. The high catalytic efficiency is attributed to the large pore size of the flower-like hierarchical flakes structure of HAM@γ-AlOOH, that gives Pd NPs on the support surface easy accessibility. Moreover, the Pd/HAM@γ-AlOOH catalyst can also be easily recycled at least five times without obvious decrease of catalytic activity. This work may provide a useful method for the fabrication of supported noble metal NP-based catalysts on the surface of mesoporous hierarchical structure materials with easy accessibility and superior activity.

Differential Multiscale Modeling of Chemically Complex Materials under Heavy Deformation: Biological, Bioinspired and Synthetic Hierarchical Materials

DTIC Science & Technology

2010-06-01

Buehler, “Meso- Origami : Folding Multilayer Graphene Sheets”, Applied Physics Letters, Vol. 95, paper #: 123121, 2009 D. Sen and M.J. Buehler, “Size and... geometry effects on flow stress in bioinspired de novo metal-matrix nanocomposites”, Advanced Engineering Materials, Vol. 11(10), pp. 774-781, 2009...behavior is recovered. Second, a subset of all geometries shows the inverse banana curve behavior. Interestingly, only 2% of all structures give the

Hierarchical Structures in Biology as a Guide for New Materials Technology

DTIC Science & Technology

1994-01-01

properties--to changes in performance requirements. For example, while the spines of the sea urchin are moving, the attached ligaments are soft and...by studying how sea urchins control the material properties of their bodies as a function of the local environment. Sea stars, sea urchins , and sea ...Materials Research Society Bulletin 16(7):23-28. Trotter, J. A., and T. J. Koob. 1989. Collagen and proteoglycan in a sea urchin ligament with mutable

Meretrix lusoria--a natural biocomposite material: in situ analysis of hierarchical fabrication and micro-hardness.

PubMed

Zhu, Zhihong; Tong, Hua; Ren, Yaoyao; Hu, Jiming

2006-01-01

The ultrastructure of clam (Meretrix lusoria) was investigated by means of scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction analyzer (XRD) combining with in situ texture decalcified technique and the micro-hardness of clam was determined, in order to understand the spatial relationship between the mineral phase and organic matrix and further explain the correlation between the property and structure. The results showed that hierarchical fabrication is the major structure character of this mollusc shell. There is specific braided structure forming from domains composed of needle-like structure made up of the single crystal of aragonite. High magnification TEM image of clam indicates the intracrystal region of the aragonite single crystal is made up of subgrain phase and some amorphous substance. There are various crystal grain growth preferential orientations in the different growth direction of the shell. An amount of organic microtubule distribute evenly in the base of calcium carbonate as reinforcement phase. The mechanical property of this natural biological composite is better than other aragonite layer of mollusc shells and pearls according to the data of micro-hardness testing. The braided structure and organic microtubule reinforcement phase are responsible for its high mechanical performance. The stereo hierarchical fabrication of clam was elucidated for the first time.

The electro-structural behaviour of yarn-like carbon nanotube fibres immersed in organic liquids

NASA Astrophysics Data System (ADS)

Terrones, Jeronimo; Windle, Alan H.; Elliott, James A.

2014-10-01

Yarn-like carbon nanotube (CNT) fibres are a hierarchically-structured material with a variety of promising applications such as high performance composites, sensors and actuators, smart textiles, and energy storage and transmission. However, in order to fully realize these possibilities, a more detailed understanding of their interactions with the environment is required. In this work, we describe a simplified representation of the hierarchical structure of the fibres from which several mathematical models are constructed to explain electro-structural interactions of fibres with organic liquids. A balance between the elastic and surface energies of the CNT bundle network in different media allows the determination of the maximum lengths that open junctions can sustain before collapsing to minimize the surface energy. This characteristic length correlates well with the increase of fibre resistance upon immersion in organic liquids. We also study the effect of charge accumulation in open interbundle junctions and derive expressions to describe experimental data on the non-ohmic electrical behaviour of fibres immersed in polar liquids. Our analyses suggest that the non-ohmic behaviour is caused by progressively shorter junctions collapsing as the voltage is increased. Since our models are not based on any property unique to carbon nanotubes, they should also be useful to describe other hierarchical structures.

Nanoparticles and self-organisation: the emergence of hierarchical properties from the nanoparticle soup (i.e., the small is getting bigger). Concluding remarks for Faraday Discussion: Nanoparticle Synthesis and Assembly.

PubMed

Schiffrin, David J

2015-01-01

Some four years ago, one of the participants in this Discussion (Prof. Nicholas Kotov) predicted that: "within five years we shall see multiple examples of electronic, sensor, optical and other devices utilizing self-assembled superstructures" (N. A. Kotov, J. Mater. Chem., 2011, 21, 16673-16674). Although this prediction came partially to fruition, we have witnessed an unprecedented interest in the properties of materials at the nanoscale. The point highlighted by Kotov, however, was the importance of self-assembly of structures from well characterised building blocks to yield hierarchical structures, hopefully with predictable properties, a concept that is an everyday pursuit of synthetic chemists. This Discussion has brought together researchers from a wide range of disciplines, i.e., colloid science, modelling, nanoparticle synthesis and organisation, magnetic and optical materials, and new imaging methods, within the excellent traditional Faraday Discussion format, to discuss advances in areas relevant to the main theme of the meeting.

Chiral nematic self-assembly of minimally surface damaged chitin nanofibrils and its load bearing functions

PubMed Central

Oh, Dongyeop X.; Cha, Yun Jeong; Nguyen, Hoang-Linh; Je, Hwa Heon; Jho, Yong Seok; Hwang, Dong Soo; Yoon, Dong Ki

2016-01-01

Chitin is one of the most abundant biomaterials in nature, with 1010 tons produced annually as hierarchically organized nanofibril fillers to reinforce the exoskeletons of arthropods. This green and cheap biomaterial has attracted great attention due to its potential application to reinforce biomedical materials. Despite that, its practical use is limited since the extraction of chitin nanofibrils requires surface modification involving harsh chemical treatments, leading to difficulties in reproducing their natural prototypal hierarchical structure, i.e. chiral nematic phase. Here, we develop a chemical etching-free approach using calcium ions, called “natural way”, to disintegrate the chitin nanofibrils while keeping the essential moiety for the self-assembly, ultimately resulting in the reproduction of chitin’s natural chiral structure in a polymeric matrix. This chiral chitin nanostructure exceptionally toughens the composite. Our resultant chiral nematic phase of chitin materials can contribute to the understanding and use of the reinforcing strategy in nature. PMID:26988392

Materials, Structures and Manufacturing: An Integrated Approach to Develop Expandable Structures

NASA Technical Reports Server (NTRS)

Belvin, W. Keith; Zander, Martin E.; Sleight, Daid W.; Connell, John; Holloway, Nancy; Palmieri, Frank

2012-01-01

Membrane dominated space structures are lightweight and package efficiently for launch; however, they must be expanded (deployed) in-orbit to achieve the desired geometry. These expandable structural systems include solar sails, solar power arrays, antennas, and numerous other large aperture devices that are used to collect, reflect and/or transmit electromagnetic radiation. In this work, an integrated approach to development of thin-film damage tolerant membranes is explored using advanced manufacturing. Bio-inspired hierarchical structures were printed on films using additive manufacturing to achieve improved tear resistance and to facilitate membrane deployment. High precision, robust expandable structures can be realized using materials that are both space durable and processable using additive manufacturing. Test results show this initial work produced higher tear resistance than neat film of equivalent mass. Future research and development opportunities for expandable structural systems designed using an integrated approach to structural design, manufacturing, and materials selection are discussed.

Iridescent cellulose nanocrystal films: the link between structural colour and Bragg’s law

NASA Astrophysics Data System (ADS)

Nguyen, Thanh-Dinh; Sierra, Egoitz; Eguiraun, Harkaitz; Lizundia, Erlantz

2018-07-01

Structural colour is a phenomenon found in nature, which provides plants and animals with vibrant optical properties. The production of this colour is based on the interaction of incident light with the hierarchical organisation of submicron- and micron-sized layered structures. Cellulose nanocrystals (CNCs) are anisotropic building units formed by acid hydrolysis of native cellulose microfibers, which can disperse in aqueous media to form a photonic liquid crystal. One fascinating example of the appearance of biomimetic colour is the supramolecular assembly of CNCs into iridescent layered structures that rotate along a helical screw to yield a long-range chiral nematic order. A quick, simple and engaging experiment that allows the establishment of a direct relation between the structural colour and underlying mechanism of the light interaction with these hierarchically structured materials is reported. The obtained colour changes are explained within the theoretical framework provided by Bragg’s law and may provide an easy way to observe the macroscopic manifestation of this often abstract concept.

Hierarchical MoO3/SnS2 core-shell nanowires with enhanced electrochemical performance for lithium-ion batteries.

PubMed

Hu, Chenli; Shu, Haibo; Shen, Zihong; Zhao, Tianfeng; Liang, Pei; Chen, Xiaoshuang

2018-06-27

Two-dimensional (2D) tin disulfide (SnS2) is a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity. The main challenges associated with the SnS2 electrodes are the poor cycling stability and low rate capability due to structural degradation in the discharge/charge process. Here, a facile two-step synthesis method is developed to fabricate hierarchical MoO3/SnS2 core-shell nanowires, where ultrathin SnS2 nanosheets are vertically anchored on MoO3 nanobelts to induce a heterointerface. Benefiting from the unique structural and compositional characteristics, the hierarchical MoO3/SnS2 core-shell nanowires exhibit excellent electrochemical performance and deliver a high reversible capacity of 504 mA h g-1 after 100 stable cycles at a current density of 100 mA g-1, which is far superior to the MoO3 and SnS2 electrodes. An analysis of lithiation dynamics based on ab initio molecular dynamics simulations demonstrates that the formation of a hierarchical MoO3/SnS2 core-shell heterostructure can effectively suppress the rapid dissociation of shell-layer SnS2 nanosheets via the interfacial coupling effect and the central MoO3 backbone can trap and support the polysulfide in the discharge/charge process. The results are responsible for the high storage capacity and rate capability of MoO3/SnS2 electrode materials. This work provides a novel design strategy for constructing high-performance electrodes for LIBs.

Regeneration of high-quality silk fibroin fiber by wet spinning from CaCl2-formic acid solvent.

PubMed

Zhang, Feng; Lu, Qiang; Yue, Xiaoxiao; Zuo, Baoqi; Qin, Mingde; Li, Fang; Kaplan, David L; Zhang, Xueguang

2015-01-01

Silks spun by silkworms and spiders feature outstanding mechanical properties despite being spun under benign conditions. The superior physical properties of silk are closely related to its complicated hierarchical structures constructed from nanoscale building blocks, such as nanocrystals and nanofibrils. Here, we report a novel silk dissolution behavior, which preserved nanofibrils in CaCl2-formic acid solution, that enables spinning of high-quality fibers with a hierarchical structure. This process is characterized by simplicity, high efficiency, low cost, environmental compatibility and large-scale industrialization potential, as well as having utility and potential for the recycling of silk waste and the production of silk-based functional materials. Copyright © 2014. Published by Elsevier Ltd.

Convenient and large-scale synthesis of nitrogen-rich hierarchical porous carbon spheres for supercapacitors and CO2 capture

NASA Astrophysics Data System (ADS)

Chang, Binbin; Zhang, Shouren; Yin, Hang; Yang, Baocheng

2017-08-01

Herein, considering the great potential of nitrogen-doped hierarchical porous carbons in energy storage and CO2 capture, we designed a convenient and easily large-scale production strategy for preparing nitrogen-doped hierarchical porous carbon sphere (NHPCS) materials. In this synthesis route, spherical resorcinol-formaldehyde (RF) resins were selected as carbon precursor, and then the ZnCl2-impregnated RF resin spheres were carbonized in a NH3 atmosphere at a temperature range of 600-800 °C. During the one-step heat-treatment process, nitrogen atom could be efficiently incorporated into the carbon skeleton, and the interconnected and hierarchical pore structure with different micro/mesopore proportion could be generated and tuned by adjusting the activating agent ZnCl2 dosage and carbonization temperature. The resultant nitrogen-doped hierarchical porous carbon sphere materials exhibited a satisfactory charge storage capacity, and the optimal sample of NHPCS-2-8 with a high mesopore proportion obtained at 800 °C with a ZnCl2/RF mass ratio of 2:1 presented a specific capacitance of 273.8 F g-1 at a current density of 0.5 A g-1. More importantly, the assembled NHPCS-2-8-based symmetric capacitor displayed a high energy density of 17.2 Wh kg-1 at a power density of 178.9 W kg-1 within a voltage window of 0 ∼ 1.8 V in 0.5 M Na2SO4 aqueous electrolyte. In addition, the CO2 capture application of these NHPCS materials was also explored, and the optimal sample of NHPCS-0-8 with a large micropore proportion prepared at 800 °C exhibited an exceptional CO2 uptake capacity at ambient pressures of up to 4.23 mmol g-1 at 0 °C.

PEDOT-PSS coated ZnO/C hierarchical porous nanorods as ultralong-life anode material for lithium ion batteries

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

Xu, Gui-Liang; Li, Yan; Ma, Tianyuan

2015-11-01

ZnO/C hierarchical porous nanorods were synthesized through one-pot wet-chemical reaction followed by thermal calcination. It was found that ZnO/C porous nanorods are composed of numerous nanograins, exhibiting a hierarchical micro/nanostructure. In-situ synchrotron high energy X-ray diffraction study revealed that ZnO/C hierarchical porous nanorods involve a two-step reversible lithiation mechanism during charge/discharge; and part of ZnO and Zn remains at the end of the first discharge and charge process, respectively, leading to a low coulombic efficiency in the initial few cycles. The electrochemical test demonstrated that the reversible capacity and the rate performance of ZnO/C hierarchical porous nanorods anode have beenmore » greatly improved by PEDOT-PSS coating, which could maintain a reversible capacity of 623.94 mA h g(-1) after 1500 cycles at 1 C. Its excellent high rate capability and long cycle stability were attributed to the high electronic conductivity of PEDOT-PSS coating layer and the hierarchical structures of ZnO/C porous nanorods. (C) 2015 Elsevier Ltd. All rights reserved.« less

High electrochemical performances of hierarchical hydrangea macrophylla like NiCo{sub 2}O{sub 4} and NiCo{sub 2}S{sub 4} as anode materials for Li-ion batteries

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

Jin, Rencheng, E-mail: jinrc427@126.com; Liu, Gang; Liu, Chunping

2016-08-15

Graphical abstract: Mesoporous hydrangea macrophylla like NiCo{sub 2}O{sub 4} and NiCo{sub 2}S{sub 4} have been fabricated, which present excellent electrochemical performances as anode materials for Li-ion batteries. - Highlights: • Hierarchical NiCo{sub 2}O{sub 4} is successfully fabricated. • Hierarchical NiCo{sub 2}S{sub 4} is prepared via sulfide anion exchange. • The hierarchical NiCo{sub 2}O{sub 4} and NiCo{sub 2}S{sub 4} exhibit good electrochemical properties. - Abstract: In this work, hierarchical hydrangea macrophylla like NiCo{sub 2}O{sub 4} has been synthesized by solvothermal method followed by calcination treatment in air. By using Na{sub 2}S as sulfur source, the NiCo{sub 2}O{sub 4} is converted intomore » NiCo{sub 2}S{sub 4}. Such hierarchical NiCo{sub 2}O{sub 4} exhibits a high specific capacity and excellent cycling stability (928 mAh g{sup −1} at a current density of 100 mA g{sup −1} after 100 cycles). Even at high current density of 2000 mA g{sup −1}, the electrode still delivers a specific capacity of 371 mAh g{sup −1} after 50 cycles. When the NiCo{sub 2}S{sub 4} is used as anode materials for lithium-ion batteries, a high discharge capacity of 1204 mAh g{sup −1} can be achieved. Meanwhile, the NiCo{sub 2}S{sub 4} electrode displays good cycling stability and rate capability. The excellent electrochemical performances can be attributed to the unique porous structure, which can effectively reduce the diffusion length for lithium ions and electrons, and alleviate volume expansion during the charge-discharge processes.« less

Collective helicity switching of a DNA-coat assembly

NASA Astrophysics Data System (ADS)

Kim, Yongju; Li, Huichang; He, Ying; Chen, Xi; Ma, Xiaoteng; Lee, Myongsoo

2017-07-01

Hierarchical assemblies of biomolecular subunits can carry out versatile tasks at the cellular level with remarkable spatial and temporal precision. As an example, the collective motion and mutual cooperation between complex protein machines mediate essential functions for life, such as replication, synthesis, degradation, repair and transport. Nucleic acid molecules are far less dynamic than proteins and need to bind to specific proteins to form hierarchical structures. The simplest example of these nucleic acid-based structures is provided by a rod-shaped tobacco mosaic virus, which consists of genetic material surrounded by coat proteins. Inspired by the complexity and hierarchical assembly of viruses, a great deal of effort has been devoted to design similarly constructed artificial viruses. However, such a wrapping approach makes nucleic acid dynamics insensitive to environmental changes. This limitation generally restricts, for example, the amplification of the conformational dynamics between the right-handed B form to the left-handed Z form of double-stranded deoxyribonucleic acid (DNA). Here we report a virus-like hierarchical assembly in which the native DNA and a synthetic coat undergo repeated collective helicity switching triggered by pH change under physiological conditions. We also show that this collective helicity inversion occurs during translocation of the DNA-coat assembly into intracellular compartments. Translating DNA conformational dynamics into a higher level of hierarchical dynamics may provide an approach to create DNA-based nanomachines.

Tribology of bio-inspired nanowrinkled films on ultrasoft substrates.

PubMed

Lackner, Juergen M; Waldhauser, Wolfgang; Major, Lukasz; Teichert, Christian; Hartmann, Paul

2013-01-01

Biomimetic design of new materials uses nature as antetype, learning from billions of years of evolution. This work emphasizes the mechanical and tribological properties of skin, combining both hardness and wear resistance of its surface (the stratum corneum) with high elasticity of the bulk (epidermis, dermis, hypodermis). The key for combination of such opposite properties is wrinkling, being consequence of intrinsic stresses in the bulk (soft tissue): Tribological contact to counterparts below the stress threshold for tissue trauma occurs on the thick hard stratum corneum layer pads, while tensile loads smooth out wrinkles in between these pads. Similar mechanism offers high tribological resistance to hard films on soft, flexible polymers, which is shown for diamond-like carbon (DLC) and titanium nitride thin films on ultrasoft polyurethane and harder polycarbonate substrates. The choice of these two compared substrate materials will show that ultra-soft substrate materials are decisive for the distinct tribological material. Hierarchical wrinkled structures of films on these substrates are due to high intrinsic compressive stress, which evolves during high energetic film growth. Incremental relaxation of these stresses occurs by compound deformation of film and elastic substrate surface, appearing in hierarchical nano-wrinkles. Nano-wrinkled topographies enable high elastic deformability of thin hard films, while overstressing results in zigzag film fracture along larger hierarchical wrinkle structures. Tribologically, these fracture mechanisms are highly important for ploughing and sliding of sharp and flat counterparts on hard-coated ultra-soft substrates like polyurethane. Concentration of polyurethane deformation under the applied normal loads occurs below these zigzag cracks. Unloading closes these cracks again. Even cyclic testing do not lead to film delamination and retain low friction behavior, if the adhesion to the substrate is high and the initial friction coefficient of the film against the sliding counterpart low, e.g. found for DLC.

Tribology of bio-inspired nanowrinkled films on ultrasoft substrates

PubMed Central

Lackner, Juergen M.; Waldhauser, Wolfgang; Major, Lukasz; Teichert, Christian; Hartmann, Paul

2013-01-01

Biomimetic design of new materials uses nature as antetype, learning from billions of years of evolution. This work emphasizes the mechanical and tribological properties of skin, combining both hardness and wear resistance of its surface (the stratum corneum) with high elasticity of the bulk (epidermis, dermis, hypodermis). The key for combination of such opposite properties is wrinkling, being consequence of intrinsic stresses in the bulk (soft tissue): Tribological contact to counterparts below the stress threshold for tissue trauma occurs on the thick hard stratum corneum layer pads, while tensile loads smooth out wrinkles in between these pads. Similar mechanism offers high tribological resistance to hard films on soft, flexible polymers, which is shown for diamond-like carbon (DLC) and titanium nitride thin films on ultrasoft polyurethane and harder polycarbonate substrates. The choice of these two compared substrate materials will show that ultra-soft substrate materials are decisive for the distinct tribological material. Hierarchical wrinkled structures of films on these substrates are due to high intrinsic compressive stress, which evolves during high energetic film growth. Incremental relaxation of these stresses occurs by compound deformation of film and elastic substrate surface, appearing in hierarchical nano-wrinkles. Nano-wrinkled topographies enable high elastic deformability of thin hard films, while overstressing results in zigzag film fracture along larger hierarchical wrinkle structures. Tribologically, these fracture mechanisms are highly important for ploughing and sliding of sharp and flat counterparts on hard-coated ultra-soft substrates like polyurethane. Concentration of polyurethane deformation under the applied normal loads occurs below these zigzag cracks. Unloading closes these cracks again. Even cyclic testing do not lead to film delamination and retain low friction behavior, if the adhesion to the substrate is high and the initial friction coefficient of the film against the sliding counterpart low, e.g. found for DLC. PMID:24688710

Effects of different hierarchical hybrid micro/nanostructure surfaces on implant osseointegration.

PubMed

Cheng, Bingkun; Niu, Qiang; Cui, Yajun; Jiang, Wei; Zhao, Yunzhuan; Kong, Liang

2017-06-01

Hierarchical hybrid micro/nanostructure implant surfaces are considered to better mimic the hierarchical structure of bone and the nanostructures substantively influence osseointegration through managing cell behaviors. To enhance implant osseointegration for further clinical application, we evaluated the material properties and osseointegration effects of hierarchical surfaces with different nano-morphologies, using a rat model. Two representative surface fabrication methods, hydrofluoric (HF) acid etching combined with anodization (HF + AN) or magnetron sputtering (HF + MS), were selected. Sample material properties were evaluated by scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoemission spectroscopy, and epoxy resin docking tensile test. Implants with different surfaces were inserted into the distal femurs of rats. After 12 weeks, osseointegration was examined by microcomputed tomography (micro-CT), histological, and biomechanical tests. Tensile testing demonstrated high bonding strength at coating/implant in the HF + MS group. Micro-CT revealed increased bone volume/total volume and significantly reduced trabecular separation in HF + MS versus other groups. Histological analysis showed significantly higher HF + MS bone-to-implant contact (74.78 ± 4.40%) versus HF + AN (65.11 ± 5.10%) and machined samples (56.03 ± 3.23%). The maximal HF + MS pull-out force increased by 33.7% versus HF + AN. These results indicated that HF + MS surfaces exhibited superior material property in terms of bonding strength and favorable implant osseointegration compared to other groups. © 2017 Wiley Periodicals, Inc.

Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics

PubMed Central

Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud; Cheng, Jing; Barrett, Devin G.; Guan, Zhibin; Messersmith, Phillip B.; Holten-Andersen, Niels

2015-01-01

In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure may inform the design of soft materials for use in complex mechanical environments. PMID:26322715

Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks

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

Dolgopolova, Ekaterina A.; Ejegbavwo, Otega A.; Martin, Corey R.

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures towards fundamental understanding of mechanisms involved in actinide integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials were built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with “unsaturated” metal nodes. The first successfulmore » attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt% in mono- and bi-actinide frameworks with minimal structural density. Overall, combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions could make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures, and therefore, shed light on possible optimization of nuclear waste administration.« less

Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal-Organic Frameworks.

PubMed

Dolgopolova, Ekaterina A; Ejegbavwo, Otega A; Martin, Corey R; Smith, Mark D; Setyawan, Wahyu; Karakalos, Stavros G; Henager, Charles H; Zur Loye, Hans-Conrad; Shustova, Natalia B

2017-11-22

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures toward fundamental understanding of mechanisms involved in actinide (An) integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials was built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with "unsaturated" metal nodes. The first successful attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt % in mono- and biactinide frameworks with minimal structural density. Overall, the combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions could make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures and, therefore, shed light on possible optimization of nuclear waste administration.

A nonlinear mechanics model of bio-inspired hierarchical lattice materials consisting of horseshoe microstructures

PubMed Central

Ma, Qiang; Cheng, Huanyu; Jang, Kyung-In; Luan, Haiwen; Hwang, Keh-Chih; Rogers, John A.; Huang, Yonggang; Zhang, Yihui

2016-01-01

Development of advanced synthetic materials that can mimic the mechanical properties of non-mineralized soft biological materials has important implications in a wide range of technologies. Hierarchical lattice materials constructed with horseshoe microstructures belong to this class of bio-inspired synthetic materials, where the mechanical responses can be tailored to match the nonlinear J-shaped stress-strain curves of human skins. The underlying relations between the J-shaped stress-strain curves and their microstructure geometry are essential in designing such systems for targeted applications. Here, a theoretical model of this type of hierarchical lattice material is developed by combining a finite deformation constitutive relation of the building block (i.e., horseshoe microstructure), with the analyses of equilibrium and deformation compatibility in the periodical lattices. The nonlinear J-shaped stress-strain curves and Poisson ratios predicted by this model agree very well with results of finite element analyses (FEA) and experiment. Based on this model, analytic solutions were obtained for some key mechanical quantities, e.g., elastic modulus, Poisson ratio, peak modulus, and critical strain around which the tangent modulus increases rapidly. A negative Poisson effect is revealed in the hierarchical lattice with triangular topology, as opposed to a positive Poisson effect in hierarchical lattices with Kagome and honeycomb topologies. The lattice topology is also found to have a strong influence on the stress-strain curve. For the three isotropic lattice topologies (triangular, Kagome and honeycomb), the hierarchical triangular lattice material renders the sharpest transition in the stress-strain curve and relative high stretchability, given the same porosity and arc angle of horseshoe microstructure. Furthermore, a demonstrative example illustrates the utility of the developed model in the rapid optimization of hierarchical lattice materials for reproducing the desired stress-strain curves of human skins. This study provides theoretical guidelines for future designs of soft bio-mimetic materials with hierarchical lattice constructions. PMID:27087704

A nonlinear mechanics model of bio-inspired hierarchical lattice materials consisting of horseshoe microstructures

NASA Astrophysics Data System (ADS)

Ma, Qiang; Cheng, Huanyu; Jang, Kyung-In; Luan, Haiwen; Hwang, Keh-Chih; Rogers, John A.; Huang, Yonggang; Zhang, Yihui

2016-05-01

Development of advanced synthetic materials that can mimic the mechanical properties of non-mineralized soft biological materials has important implications in a wide range of technologies. Hierarchical lattice materials constructed with horseshoe microstructures belong to this class of bio-inspired synthetic materials, where the mechanical responses can be tailored to match the nonlinear J-shaped stress-strain curves of human skins. The underlying relations between the J-shaped stress-strain curves and their microstructure geometry are essential in designing such systems for targeted applications. Here, a theoretical model of this type of hierarchical lattice material is developed by combining a finite deformation constitutive relation of the building block (i.e., horseshoe microstructure), with the analyses of equilibrium and deformation compatibility in the periodical lattices. The nonlinear J-shaped stress-strain curves and Poisson ratios predicted by this model agree very well with results of finite element analyses (FEA) and experiment. Based on this model, analytic solutions were obtained for some key mechanical quantities, e.g., elastic modulus, Poisson ratio, peak modulus, and critical strain around which the tangent modulus increases rapidly. A negative Poisson effect is revealed in the hierarchical lattice with triangular topology, as opposed to a positive Poisson effect in hierarchical lattices with Kagome and honeycomb topologies. The lattice topology is also found to have a strong influence on the stress-strain curve. For the three isotropic lattice topologies (triangular, Kagome and honeycomb), the hierarchical triangular lattice material renders the sharpest transition in the stress-strain curve and relative high stretchability, given the same porosity and arc angle of horseshoe microstructure. Furthermore, a demonstrative example illustrates the utility of the developed model in the rapid optimization of hierarchical lattice materials for reproducing the desired stress-strain curves of human skins. This study provides theoretical guidelines for future designs of soft bio-mimetic materials with hierarchical lattice constructions.

A nonlinear mechanics model of bio-inspired hierarchical lattice materials consisting of horseshoe microstructures.

PubMed

Ma, Qiang; Cheng, Huanyu; Jang, Kyung-In; Luan, Haiwen; Hwang, Keh-Chih; Rogers, John A; Huang, Yonggang; Zhang, Yihui

2016-05-01

Development of advanced synthetic materials that can mimic the mechanical properties of non-mineralized soft biological materials has important implications in a wide range of technologies. Hierarchical lattice materials constructed with horseshoe microstructures belong to this class of bio-inspired synthetic materials, where the mechanical responses can be tailored to match the nonlinear J-shaped stress-strain curves of human skins. The underlying relations between the J-shaped stress-strain curves and their microstructure geometry are essential in designing such systems for targeted applications. Here, a theoretical model of this type of hierarchical lattice material is developed by combining a finite deformation constitutive relation of the building block (i.e., horseshoe microstructure), with the analyses of equilibrium and deformation compatibility in the periodical lattices. The nonlinear J-shaped stress-strain curves and Poisson ratios predicted by this model agree very well with results of finite element analyses (FEA) and experiment. Based on this model, analytic solutions were obtained for some key mechanical quantities, e.g., elastic modulus, Poisson ratio, peak modulus, and critical strain around which the tangent modulus increases rapidly. A negative Poisson effect is revealed in the hierarchical lattice with triangular topology, as opposed to a positive Poisson effect in hierarchical lattices with Kagome and honeycomb topologies. The lattice topology is also found to have a strong influence on the stress-strain curve. For the three isotropic lattice topologies (triangular, Kagome and honeycomb), the hierarchical triangular lattice material renders the sharpest transition in the stress-strain curve and relative high stretchability, given the same porosity and arc angle of horseshoe microstructure. Furthermore, a demonstrative example illustrates the utility of the developed model in the rapid optimization of hierarchical lattice materials for reproducing the desired stress-strain curves of human skins. This study provides theoretical guidelines for future designs of soft bio-mimetic materials with hierarchical lattice constructions.

Biomimetic Structural Materials: Inspiration from Design and Assembly.

PubMed

Yaraghi, Nicholas A; Kisailus, David

2018-04-20

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

Biomimetic Structural Materials: Inspiration from Design and Assembly

NASA Astrophysics Data System (ADS)

Yaraghi, Nicholas A.; Kisailus, David

2018-04-01

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

Facile synthesis of three dimensional hierarchical Co-Al layered double hydroxides on graphene as high-performance materials for supercapacitor electrode.

PubMed

Hao, Jinhui; Yang, Wenshu; Zhang, Zhe; Lu, Baoping; Ke, Xi; Zhang, Bailin; Tang, Jilin

2014-07-15

A facile simple hydrothermal method combined with a post-solution reaction is developed to grow interconnected three dimensional (3D) hierarchical Co-Al layered double hydroxides (LDHs) on reduced graphene oxide (rGO). The obtained 3D hierarchical rGO-LDHs are characterized by field emission scanning electron microscopy, X-ray diffraction, and X-ray photo-electron spectroscopy. As LDHs nanosheets directly grow on the surface of rGO via chemical covalent bonding, the rGO could provide facile electron transport paths in the electrode for the fast Faradaic reaction. Moreover, benefiting from the rational 3D hierarchical structural, the rGO-LDHs demonstrate excellent electrochemical properties with a combination of high charge storage capacitance, fast rate capability and stable cycling performance. Remarkably, the 3D hierarchical rGO-LDHs exhibit specific capacitance values of 599 F g(-1) at a constant current density of 4 A g(-1). The rGO-LDHs also show high charge-discharge reversibility with an efficiency of 92.4% after 5000 cycles. Copyright © 2014 Elsevier Inc. All rights reserved.

Controlled Fabrication of Silk Protein Sericin Mediated Hierarchical Hybrid Flowers and Their Excellent Adsorption Capability of Heavy Metal Ions of Pb(II), Cd(II) and Hg(II).

PubMed

Koley, Pradyot; Sakurai, Makoto; Aono, Masakazu

2016-01-27

Fabrication of protein-inorganic hybrid materials of innumerable hierarchical patterns plays a major role in the development of multifunctional advanced materials with their improved features in synergistic way. However, effective fabrication and applications of the hybrid structures is limited due to the difficulty in control and production cost. Here, we report the controlled fabrication of complex hybrid flowers with hierarchical porosity through a green and facile coprecipitation method by using industrial waste natural silk protein sericin. The large surface areas and porosity of the microsize hybrid flowers enable water purification through adsorption of different heavy metal ions. The high adsorption capacity depends on their morphology, which is changed largely by sericin concentration in their fabrication. Superior adsorption and greater selectivity of the Pb(II) ions have been confirmed by the characteristic growth of needle-shaped nanowires on the hierarchical surface of the hybrid flowers. These hybrid flowers show excellent thermal stability even after complete evaporation of the protein molecules, significantly increasing the porosity of the flower petals. A simple, cost-effective and environmental friendly fabrication method of the porous flowers will lead to a new solution to water pollution required in the modern industrial society.

Structure-property relationships of a biological mesocrystal in the adult sea urchin spine

PubMed Central

Seto, Jong; Ma, Yurong; Davis, Sean A.; Meldrum, Fiona; Gourrier, Aurelien; Kim, Yi-Yeoun; Schilde, Uwe; Sztucki, Michael; Burghammer, Manfred; Maltsev, Sergey; Jäger, Christian; Cölfen, Helmut

2012-01-01

Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature’s demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials. PMID:22343283

Structure-property relationships of a biological mesocrystal in the adult sea urchin spine.

PubMed

Seto, Jong; Ma, Yurong; Davis, Sean A; Meldrum, Fiona; Gourrier, Aurelien; Kim, Yi-Yeoun; Schilde, Uwe; Sztucki, Michael; Burghammer, Manfred; Maltsev, Sergey; Jäger, Christian; Cölfen, Helmut

2012-03-06

Structuring over many length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, show how Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature's demonstration of how crystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials.

Engineering the shape and structure of materials by fractal cut.

PubMed

Cho, Yigil; Shin, Joong-Ho; Costa, Avelino; Kim, Tae Ann; Kunin, Valentin; Li, Ju; Lee, Su Yeon; Yang, Shu; Han, Heung Nam; Choi, In-Suk; Srolovitz, David J

2014-12-09

In this paper we discuss the transformation of a sheet of material into a wide range of desired shapes and patterns by introducing a set of simple cuts in a multilevel hierarchy with different motifs. Each choice of hierarchical cut motif and cut level allows the material to expand into a unique structure with a unique set of properties. We can reverse-engineer the desired expanded geometries to find the requisite cut pattern to produce it without changing the physical properties of the initial material. The concept was experimentally realized and applied to create an electrode that expands to >800% the original area with only very minor stretching of the underlying material. The generality of our approach greatly expands the design space for materials so that they can be tuned for diverse applications.

Construct 3D porous hollow Co3O4 micro-sphere: A potential oxidizer of nano-energetic materials with superior reactivity

NASA Astrophysics Data System (ADS)

Wang, Jun; Zheng, Bo; Qiao, Zhiqiang; Chen, Jin; Zhang, Liyuan; Zhang, Long; Li, Zhaoqian; Zhang, Xingquan; Yang, Guangcheng

2018-06-01

High energy density and rapid reactivity are the future trend for nano-energetic materials. Energetic performance of nano-energetic materials depends on the interfacial diffusion and mass transfer during the reacted process. However, the development of desired structure to significantly enhance reactivity still remains challenging. Here we focused on the design and preparation of 3D porous hollow Co3O4 micro-spheres, in which gas-blowing agents (air) and maximize interfacial interactions were introduced to enhance mass transport and reduce the diffusion distance between the oxidizer and fuel (Aluminum). The 3D hierarchical Co3O4/Al based nano-energetic materials show a low-onset decomposition temperature (423 °C), and high heat output (3118 J g-1) resulting from porous and hollow nano-structure of Co3O4 micro-spheres. Furthermore, 3D hierarchical Co3O4/Al arrays were directly fabricated on the silicon substrate, which was fully compatible with silicon-based microelectromechanical systems to achieve functional nanoenergetics-on-a-chip. This approach provides a simple and efficient way to fabricate 3D ordered nano-energetic arrays with superior reactivity and the potential on the application in micro-energetic devices.

Nature-Inspired Structural Materials for Flexible Electronic Devices.

PubMed

Liu, Yaqing; He, Ke; Chen, Geng; Leow, Wan Ru; Chen, Xiaodong

2017-10-25

Exciting advancements have been made in the field of flexible electronic devices in the last two decades and will certainly lead to a revolution in peoples' lives in the future. However, because of the poor sustainability of the active materials in complex stress environments, new requirements have been adopted for the construction of flexible devices. Thus, hierarchical architectures in natural materials, which have developed various environment-adapted structures and materials through natural selection, can serve as guides to solve the limitations of materials and engineering techniques. This review covers the smart designs of structural materials inspired by natural materials and their utility in the construction of flexible devices. First, we summarize structural materials that accommodate mechanical deformations, which is the fundamental requirement for flexible devices to work properly in complex environments. Second, we discuss the functionalities of flexible devices induced by nature-inspired structural materials, including mechanical sensing, energy harvesting, physically interacting, and so on. Finally, we provide a perspective on newly developed structural materials and their potential applications in future flexible devices, as well as frontier strategies for biomimetic functions. These analyses and summaries are valuable for a systematic understanding of structural materials in electronic devices and will serve as inspirations for smart designs in flexible electronics.

Measuring the hierarchy of feedforward networks

NASA Astrophysics Data System (ADS)

Corominas-Murtra, Bernat; Rodríguez-Caso, Carlos; Goñi, Joaquín; Solé, Ricard

2011-03-01

In this paper we explore the concept of hierarchy as a quantifiable descriptor of ordered structures, departing from the definition of three conditions to be satisfied for a hierarchical structure: order, predictability, and pyramidal structure. According to these principles, we define a hierarchical index taking concepts from graph and information theory. This estimator allows to quantify the hierarchical character of any system susceptible to be abstracted in a feedforward causal graph, i.e., a directed acyclic graph defined in a single connected structure. Our hierarchical index is a balance between this predictability and pyramidal condition by the definition of two entropies: one attending the onward flow and the other for the backward reversion. We show how this index allows to identify hierarchical, antihierarchical, and nonhierarchical structures. Our formalism reveals that departing from the defined conditions for a hierarchical structure, feedforward trees and the inverted tree graphs emerge as the only causal structures of maximal hierarchical and antihierarchical systems respectively. Conversely, null values of the hierarchical index are attributed to a number of different configuration networks; from linear chains, due to their lack of pyramid structure, to full-connected feedforward graphs where the diversity of onward pathways is canceled by the uncertainty (lack of predictability) when going backward. Some illustrative examples are provided for the distinction among these three types of hierarchical causal graphs.

Social Bookmarking on a Company's Intranet: A Study of Technology Adoption and Diffusion

NASA Astrophysics Data System (ADS)

Ziv, Nina D.; White, Kerry-Ann

Until recent developments in digital-based innovation, companies were defined by how they made use of resources which were tangible things such as equipment, land, raw materials and human talent for the purpose of supplying goods and services to the economy [37]. Such companies had a clearly defined central management structure which was responsible for the general policies under which the company's hierarchy operated with well delineated reporting relationships and job responsibilities [47]. Within this rigid hierarchical organizational structure, decision making was bureaucratic and an anti-innovation bias was prevalent [55]. Even with the development of electronic communications and computing systems, innovation was relegated to the purview of professional R&D departments [22] within a highly structured corporate environment [51]. Indeed, in 1992, when managers were surveyed about the structure of their companies, most answered that their companies were still structured in a very traditional way, that is, with standardized jobs, procedures and policies and a hierarchical organization which emphasized a top-down chain of command [6].

Three-Dimensional Nanoprinting via Direct Delivery.

PubMed

Ventrici de Souza, Joao; Liu, Yang; Wang, Shuo; Dörig, Pablo; Kuhl, Tonya L; Frommer, Jane; Liu, Gang-Yu

2018-01-18

Direct writing methods are a generic and simple means to produce designed structures in three dimensions (3D). The printing is achieved by extruding printing materials through a nozzle, which provides a platform to deliver a wide range of materials. Although this method has been routinely used for 3D printing at macroscopic scales, miniaturization to micrometer and nanometer scales and building hierarchical structures at multidimensional scales represent new challenges in research and development. The current work addresses these challenges by combining the spatial precision of atomic force microscopy (AFM) and local delivery capability of microfluidics. Specialized AFM probes serve dual roles of a microscopy tip and a delivery tool, enabling the miniaturization of 3D printing via direct material delivery. Stacking grids of 20 μm periodicity were printed layer-by-layer covering 1 mm × 1 mm regions. The spatial fidelity was measured to be several nanometers, which is among the highest in 3D printing. The results clearly demonstrate the feasibility of achieving high precision 3D nanoprinting with nanometer feature size and accuracy with practical throughput and overall size. This work paves the way for advanced applications of 3D hierarchical nanostructures.

Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

PubMed

Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

2014-01-22

Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

In Situ Chelating Synthesis of Hierarchical LiNi1/3 Co1/3 Mn1/3 O2 Polyhedron Assemblies with Ultralong Cycle Life for Li-Ion Batteries.

PubMed

Zhang, Yue; Jia, Dianzeng; Tang, Yakun; Huang, Yudai; Pang, Weikong; Guo, Zaiping; Zhou, Zhen

2018-06-03

Layered lithium transition-metal oxides, with large capacity and high discharge platform, are promising cathode materials for Li-ion batteries. However, their high-rate cycling stability still remains a large challenge. Herein, hierarchical LiNi 1/3 Co 1/3 Mn 1/3 O 2 polyhedron assemblies are obtained through in situ chelation of transition metal ions (Ni 2+ , Co 2+ , and Mn 2+ ) with amide groups uniformly distributed along the backbone of modified polyacrylonitrile chains to achieve intimate mixing at the atomic level. The assemblies exhibit outstanding electrochemical performances: superior rate capability, high volumetric energy density, and especially ultralong high-rate cyclability, due to the superiority of unique hierarchical structures. The polyhedrons with exposed active crystal facets provide more channels for Li + diffusion, and meso/macropores serve as access shortcuts for fast migration of electrolytes, Li + and electrons. The strategy proposed in this work can be extended to fabricate other mixed transition metal-based materials for advanced batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seaurchin-like hierarchical NiCo2O4@NiMoO4 core-shell nanomaterials for high performance supercapacitors.

PubMed

Zhang, Qiang; Deng, Yanghua; Hu, Zhonghua; Liu, Yafei; Yao, Mingming; Liu, Peipei

2014-11-14

A novel electrode material of the three-dimensional (3D) multicomponent oxide NiCo2O4@NiMoO4 core-shell was synthesized via a facile two-step hydrothermal method using a post-annealing procedure. The uniform NiMoO4 nanosheets were grown on the seaurchin-like NiCo2O4 backbone to form a NiCo2O4@NiMoO4 core-shell material constructed by interconnected ultrathin nanosheets, so as to produce hierarchical mesopores with a large specific surface area of 100.3 m(2) g(-1). The porous feature and core-shell structure can facilitate the penetration of electrolytic ions and increases the number of electroactive sites. Hence, the NiCo2O4@NiMoO4 material exhibited a high specific capacitance of 2474 F g(-1) and 2080 F g(-1) at current densities of 1 A g(-1) and 20 A g(-1) respectively, suggesting that it has not only a very large specific capacitance, but also a good rate performance. In addition, the capacitance loss was only 5.0% after 1000 cycles of charge and discharge tests at the current density of 10 A g(-1), indicating high stability. The excellent electrochemical performance is mainly attributed to its 3D core-shell and hierarchical mesoporous structures which can provide unobstructed pathways for the fast diffusion and transportation of ions and electrons, a large number of active sites and good strain accommodation.

Facile synthesis of hierarchical porous VOx@carbon composites for supercapacitors.

PubMed

Zhao, Chunxia; Cao, Jinqiao; Yang, Yunxia; Chen, Wen; Li, Junshen

2014-08-01

Hierarchical or micro-nano structured porous VOx@carbon composites were synthesized by a one-step method using phenolic resin as the carbon precursor and ammonium metavanadate as the source of vanadium oxides. The effects of the vanadium source loading on the microstructure and electrochemical properties of the composites were investigated. X-ray diffraction results showed that as the vanadium oxides source loading increased, vanadium oxides in the composites changed oxidation states from V2O3 to mixed states of V2O3 and VO2. Electrochemical test results indicated that the micro-nano porous structure of the composites could facilitate the ion diffusion in the rich porous structure and then promote the electrochemical reaction. More importantly, we found that vanadium oxides greatly enhanced the electrochemical performance of the materials, due to the faradic capacitance generated from vanadium oxide nanoparticles. A maximum specific capacitance of 171 F/g was obtained from VOx@carbon composite with vanadium loading of ∼44 wt%. Further increasing the VOx loading over this fraction was not beneficial. Our results suggested that hierarchical porous VOx@carbon composites were promising candidates for supercapacitor applications. Copyright © 2013 Elsevier Inc. All rights reserved.

3D hierarchical porous cobalt monoxide nanoplates with a book-like structure derived from Co(CO3)0.5(OH)·0.11H2O: two-steps oriented attachment and high-performance asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Xiao, Yuanhua; Zhao, Xiaobing; Jin, Qingxian; Su, Dangcheng; Wang, Xuezhao; Wu, Shide; Zhou, Liming; Fang, Shaoming

2017-10-01

3D Hierarchical porous cobalt monoxide (CoO) nanoplates with a book-like structure derive from Co(CO3)0.5(OH)·0.11H2O by a two-steps oriented attachment mechanism in the solvothermal process. Firstly, nanoplates are formed by oriented attachment of nanorods. Secondly, new nanoplates could be generated on the old nanoplates by a sloped oriented attachment of nanorods with the based nanoplates shape into a 3D hierarchical book-like structure. The CoO nanoplates show superior specific capacitance about 1221.7 F g-1 at 1 A g-1 to most of the Co-based supercapacitor materials up to date. An asymmetric supercapacitor (ASC) based on positive electrode CoO and negative electrode active carbon (AC) exhibits an excellent energy density of 50.1 Wh kg-1 at a power density of 589 W kg-1 and gets a satisfactory cycling stability (86.3% of its initial capacitance retention at 10 A g-1 over 10 000 cycles).

3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid

PubMed Central

Dubal, Deepak P.; Aradilla, David; Bidan, Gérard; Gentile, Pascal; Schubert, Thomas J.S.; Wimberg, Jan; Sadki, Saïd; Gomez-Romero, Pedro

2015-01-01

Building of hierarchical core-shell hetero-structures is currently the subject of intensive research in the electrochemical field owing to its potential for making improved electrodes for high-performance micro-supercapacitors. Here we report a novel architecture design of hierarchical MnO2@silicon nanowires (MnO2@SiNWs) hetero-structures directly supported onto silicon wafer coupled with Li-ion doped 1-Methyl-1-propylpyrrolidinium bis(trifluromethylsulfonyl)imide (PMPyrrBTA) ionic liquids as electrolyte for micro-supercapacitors. A unique 3D mesoporous MnO2@SiNWs in Li-ion doped IL electrolyte can be cycled reversibly across a voltage of 2.2 V and exhibits a high areal capacitance of 13 mFcm−2. The high conductivity of the SiNWs arrays combined with the large surface area of ultrathin MnO2 nanoflakes are responsible for the remarkable performance of these MnO2@SiNWs hetero-structures which exhibit high energy density and excellent cycling stability. This combination of hybrid electrode and hybrid electrolyte opens up a novel avenue to design electrode materials for high-performance micro-supercapacitors. PMID:25985388

Processing of hierarchical syntactic structure in music.

PubMed

Koelsch, Stefan; Rohrmeier, Martin; Torrecuso, Renzo; Jentschke, Sebastian

2013-09-17

Hierarchical structure with nested nonlocal dependencies is a key feature of human language and can be identified theoretically in most pieces of tonal music. However, previous studies have argued against the perception of such structures in music. Here, we show processing of nonlocal dependencies in music. We presented chorales by J. S. Bach and modified versions in which the hierarchical structure was rendered irregular whereas the local structure was kept intact. Brain electric responses differed between regular and irregular hierarchical structures, in both musicians and nonmusicians. This finding indicates that, when listening to music, humans apply cognitive processes that are capable of dealing with long-distance dependencies resulting from hierarchically organized syntactic structures. Our results reveal that a brain mechanism fundamental for syntactic processing is engaged during the perception of music, indicating that processing of hierarchical structure with nested nonlocal dependencies is not just a key component of human language, but a multidomain capacity of human cognition.

From synthetic montroseite VOOH to topochemical paramontroseite VO2 and their applications in aqueous lithium ion batteries.

PubMed

Xu, Yang; Zheng, Lei; Xie, Yi

2010-11-28

Synthetic montroseite VOOH has been successfully prepared via a simple template-free hydrothermal route on a large scale for the first time-after sixty years of delay. The as-obtained sample shows a hierarchical morphology of urchin-like nanoarchitecture with hollow interiors consisting of well-crystalline nanorods standing vertically on the shell surface. Time-dependent experiments illustrated that these hierarchical hollow nanourchins were formed through the hydrolysis-driven Kirkendall effect coupled with a new-phased vanadium oxyhydroxide V(10)O(14)(OH)(2) precursor templated approach. Meanwhile, the as-obtained VOOH hollow nanourchins could convert topochemically to paramontroseite VO(2) without altering the size and original appearance during the annealing process due to the extreme structural similarity revealed by crystal structure analysis. Furthermore, the improved electrochemical performance of both montroseite VOOH and paramontroseite VO(2) hierarchical hollow structures toward Li uptake and release verifies their potential applications as anode materials in aqueous lithium ion batteries. These improved electrochemical properties could be ascribed to the synergetic effect of the microscopic tunneled crystal structure and macroscopic hollow morphological features, which provide the easy infiltration of electrolyte, short diffusion lengths for lithium ions and electron transport as well as sufficient void space to buffer the volume change.

Origin of the Reflectin Gene and Hierarchical Assembly of Its Protein.

PubMed

Guan, Zhe; Cai, Tiantian; Liu, Zhongmin; Dou, Yunfeng; Hu, Xuesong; Zhang, Peng; Sun, Xin; Li, Hongwei; Kuang, Yao; Zhai, Qiran; Ruan, Hao; Li, Xuanxuan; Li, Zeyang; Zhu, Qihui; Mai, Jingeng; Wang, Qining; Lai, Luhua; Ji, Jianguo; Liu, Haiguang; Xia, Bin; Jiang, Taijiao; Luo, Shu-Jin; Wang, Hong-Wei; Xie, Can

2017-09-25

Cephalopods, the group of animals including octopus, squid, and cuttlefish, have remarkable ability to instantly modulate body coloration and patterns so as to blend into surrounding environments [1, 2] or send warning signals to other animals [3]. Reflectin is expressed exclusively in cephalopods, filling the lamellae of intracellular Bragg reflectors that exhibit dynamic iridescence and structural color change [4]. Here, we trace the possible origin of the reflectin gene back to a transposon from the symbiotic bioluminescent bacterium Vibrio fischeri and report the hierarchical structural architecture of reflectin protein. Intrinsic self-assembly, and higher-order assembly tightly modulated by aromatic compounds, provide insights into the formation of multilayer reflectors in iridophores and spherical microparticles in leucophores and may form the basis of structural color change in cephalopods. Self-assembly and higher-order assembly in reflectin originated from a core repeating octapeptide (here named protopeptide), which may be from the same symbiotic bacteria. The origin of the reflectin gene and assembly features of reflectin protein are of considerable biological interest. The hierarchical structural architecture of reflectin and its domain and protopeptide not only provide insights for bioinspired photonic materials but also serve as unique "assembly tags" and feasible molecular platforms in biotechnology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Elaborate strategy for preparing Li4Ti5O12-based anode materials with significantly improved lithium storage: TiO2 nanodots in-situ decoration and hierarchical structure construction

NASA Astrophysics Data System (ADS)

Xu, Hui; Tian, Qinghua; Huang, Jun; Bao, Dongmei; Zhang, Zhengxi; Yang, Li

2017-11-01

Spinel Li4Ti5O12 (LTO) has attracted extensive attention as potential anode materials for power lithium-ion batteries due to its outstanding structural stability and remarkable safety. However, it's practical application yet be limited by such disadvantages of dissatisfied specific capacity, poor electron conductivity and low lithium-ion diffusion coefficient. Thus, design and preparation of LTO anodes with desirable performance is still a challenge. Herein, we have successfully and greatly improved the performance of LTO anodes, in terms of rate capability, life and specific capacity in particular via dot-to-face anatase TiO2in-situ decoration and hierarchical structure construction under a facile approach (directly using the tetrabutyl titanate as titanium source instead of specially prepared titanium oxide precursors). The as-prepared LTO-based anode (denoted as T-LTO) delivers an ultra-high reversible specific capacity of 196.5 mAh g-1 after 300 cycles at 20 mA g-1, and superior rate performance and even ultra-long life of more than 145.8 mAh g-1 at 28.5C between 1.0 and 3.0 V. The achieved outstanding electrochemical performance largely surpasses that of reportedly state-of-the-art LTO-based anode materials. This work may open up a broader vision into developing advanced LTO-based anode materials for lithium-ion batteries.

Self-Healing Nanocomposite Hydrogel with Well-Controlled Dynamic Mechanics

NASA Astrophysics Data System (ADS)

Li, Qiaochu; Mishra, Sumeet; Chen, Pangkuan; Tracy, Joseph; Holten-Andersen, Niels

Network dynamics is a crucial factor that determines the macroscopic self-healing rate and efficiency in polymeric hydrogel materials, yet its controllability is seldom studied in most reported self-healing hydrogel systems. Inspired by mussel's adhesion chemistry, we developed a novel approach to assemble inorganic nanoparticles and catechol-decorated PEG polymer into a hydrogel network. When utilized as reversible polymer-particle crosslinks, catechol-metal coordination bonds yield a unique gel network with dynamic mechanics controlled directly by interfacial crosslink structure. Taking advantage of this structure-property relationship at polymer-particle interfaces, we next designed a hierarchically structured hybrid gel with two distinct relaxation timescales. By tuning the relative contribution of the two hierarchical relaxation modes, we are able to finely control the gel's dynamic mechanical behavior from a viscoelastic fluid to a stiff solid, yet preserving its fast self-healing property without the need for external stimuli.

Predicting the Influence of Nano-Scale Material Structure on the In-Plane Buckling of Orthotropic Plates

NASA Technical Reports Server (NTRS)

Gates, Thomas S.; Odegard, Gregory M.; Nemeth, Michael P.; Frankland, Sarah-Jane V.

2004-01-01

A multi-scale analysis of the structural stability of a carbon nanotube-polymer composite material is developed. The influence of intrinsic molecular structure, such as nanotube length, volume fraction, orientation and chemical functionalization, is investigated by assessing the relative change in critical, in-plane buckling loads. The analysis method relies on elastic properties predicted using the hierarchical, constitutive equations developed from the equivalent-continuum modeling technique applied to the buckling analysis of an orthotropic plate. The results indicate that for the specific composite materials considered in this study, a composite with randomly orientated carbon nanotubes consistently provides the highest values of critical buckling load and that for low volume fraction composites, the non-functionalized nanotube material provides an increase in critical buckling stability with respect to the functionalized system.

Architected cellular ceramics with tailored stiffness via direct foam writing

NASA Astrophysics Data System (ADS)

Muth, Joseph T.; Dixon, Patrick G.; Woish, Logan; Gibson, Lorna J.; Lewis, Jennifer A.

2017-02-01

Hierarchical cellular structures are ubiquitous in nature because of their low-density, high-specific properties, and multifunctionality. Inspired by these systems, we created lightweight ceramic architectures composed of closed-cell porous struts patterned in the form of hexagonal and triangular honeycombs by direct foam writing. The foam ink contains bubbles stabilized by attractive colloidal particles suspended in an aqueous solution. The printed and sintered ceramic foam honeycombs possess low relative density (˜6%). By tailoring their microstructure and geometry, we created honeycombs with different modes of deformation, exceptional specific stiffness, and stiffness values that span over an order of magnitude. This capability represents an important step toward the scalable fabrication of hierarchical porous materials for applications, including lightweight structures, thermal insulation, tissue scaffolds, catalyst supports, and electrodes.

Architected cellular ceramics with tailored stiffness via direct foam writing

PubMed Central

Muth, Joseph T.; Dixon, Patrick G.; Woish, Logan; Gibson, Lorna J.; Lewis, Jennifer A.

2017-01-01

Hierarchical cellular structures are ubiquitous in nature because of their low-density, high-specific properties, and multifunctionality. Inspired by these systems, we created lightweight ceramic architectures composed of closed-cell porous struts patterned in the form of hexagonal and triangular honeycombs by direct foam writing. The foam ink contains bubbles stabilized by attractive colloidal particles suspended in an aqueous solution. The printed and sintered ceramic foam honeycombs possess low relative density (∼6%). By tailoring their microstructure and geometry, we created honeycombs with different modes of deformation, exceptional specific stiffness, and stiffness values that span over an order of magnitude. This capability represents an important step toward the scalable fabrication of hierarchical porous materials for applications, including lightweight structures, thermal insulation, tissue scaffolds, catalyst supports, and electrodes. PMID:28179570

Bioinspired Hierarchical Nanofibrous Silver-Nanoparticle/Anatase-Rutile-Titania Composite as an Anode Material for Lithium-Ion Batteries.

PubMed

Luo, Yan; Li, Jiao; Huang, Jianguo

2016-11-29

A new bioinspired hierarchical nanofibrous silver-nanoparticle/anatase-rutile-titania (Ag-NP/A-R-titania) composite was fabricated by employing a natural cellulose substance (e.g., commercial laboratory cellulose filter paper) as the structural scaffold template, which was composed of anatase-phase titania (A-titania) nanotubes with rutile-phase titania (R-titania) nanoneedles grown on the surfaces and further silver nanoparticles (AgNPs) immobilized thereon. As it was employed as an anode material for lithium-ion batteries (LIBs), high reversible capacity, enhanced rate performance, and excellent cycling stability were achieved as compared with those of the corresponding cellulose-substance-derived nanotubular A-titania, R-titania, heterogeneous anatase/rutile titania (A-R-titania) composite, and commercial P25 powder. This benefited from its unique porous cross-linked three-dimensional structure inherited from the initial cellulose substance scaffold, which enhances the sufficient electrode/electrolyte contact, relieves the severe volume change upon cycling, and improves the amount of lithium-ion storage; moreover, the high loading content of the silver component in the composite improves the electrical conductivity of the electrode. The structural integrity of the composite was maintained upon long-term charge/discharge cycling, indicating its significant stability.

Improving the Performance of Layered Oxide Cathode Materials with Football-Like Hierarchical Structure for Na-Ion Batteries by Incorporating Mg2+ into Vacancies in Na-Ion Layers.

PubMed

Li, Zheng-Yao; Wang, Huibo; Chen, Dongfeng; Sun, Kai; Yang, Wenyun; Yang, Jinbo; Liu, Xiangfeng; Han, Songbai

2018-04-09

The development of advanced cathode materials is still a great interest for sodium-ion batteries. The feasible commercialization of sodium-ion batteries relies on the design and exploitation of suitable electrode materials. This study offers a new insight into material design to exploit high-performance P2-type cathode materials for sodium-ion batteries. The incorporation of Mg 2+ into intrinsic Na + vacancies in Na-ion layers can lead to a high-performance P2-type cathode material for sodium-ion batteries. The materials prepared by the coprecipitation approach show a well-defined morphology of secondary football-like hierarchical structures. Neutron power diffraction and refinement results demonstrate that the incorporation of Mg 2+ into intrinsic vacancies can enlarge the space for Na-ion diffusion, which can increase the d-spacing of the (0 0 2) peak and the size of slabs but reduce the chemical bond length to result in an enhanced rate capability and cycling stability. The incorporation of Mg 2+ into available vacancies and a unique morphology make Na 0.7 Mg 0.05 Mn 0.8 Ni 0.1 Co 0.1 O 2 a promising cathode, which can be charged and discharged at an ultra-high current density of 2000 mA g -1 with an excellent specific capacity of 60 mAh g -1 . This work provides a new insight into the design of electrode materials for sodium-ion batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-cleaning poly(dimethylsiloxane) film with functional micro/nano hierarchical structures.

PubMed

Zhang, Xiao-Sheng; Zhu, Fu-Yun; Han, Meng-Di; Sun, Xu-Ming; Peng, Xu-Hua; Zhang, Hai-Xia

2013-08-27

This paper reports a novel single-step wafer-level fabrication of superhydrophobic micro/nano dual-scale (MNDS) poly(dimethylsiloxane) (PDMS) films. The MNDS PDMS films were replicated directly from an ultralow-surface-energy silicon substrate at high temperature without any surfactant coating, achieving high precision. An improved deep reactive ion etching (DRIE) process with enhanced passivation steps was proposed to easily realize the ultralow-surface-energy MNDS silicon substrate and also utilized as a post-treatment process to strengthen the hydrophobicity of the MNDS PDMS film. The chemical modification of this enhanced passivation step to the surface energy has been studied by density functional theory, which is also the first investigation of C4F8 plasma treatment at molecular level by using first-principle calculations. From the results of a systematic study on the effect of key process parameters (i.e., baking temperature and time) on PDMS replication, insight into the interaction of hierarchical multiscale structures of polymeric materials during the micro/nano integrated fabrication process is experimentally obtained for the first time. Finite element simulation has been employed to illustrate this new phenomenon. Additionally, hierarchical PDMS pyramid arrays and V-shaped grooves have been developed and are intended for applications as functional structures for a light-absorption coating layer and directional transport of liquid droplets, respectively. This stable, self-cleaning PDMS film with functional micro/nano hierarchical structures, which is fabricated through a wafer-level single-step fabrication process using a reusable silicon mold, shows attractive potential for future applications in micro/nanodevices, especially in micro/nanofluidics.

Design of a structural and functional hierarchy for planning and control of telerobotic systems

NASA Technical Reports Server (NTRS)

Acar, Levent; Ozguner, Umit

1989-01-01

Hierarchical structures offer numerous advantages over conventional structures for the control of telerobotic systems. A hierarchically organized system can be controlled via undetailed task assignments and can easily adapt to changing circumstances. The distributed and modular structure of these systems also enables fast response needed in most telerobotic applications. On the other hand, most of the hierarchical structures proposed in the literature are based on functional properties of a system. These structures work best for a few given functions of a large class of systems. In telerobotic applications, all functions of a single system needed to be explored. This approach requires a hierarchical organization based on physical properties of a system and such a hierarchical organization is introduced. The decomposition, organization, and control of the hierarchical structure are considered, and a system with two robot arms and a camera is presented.

Uniting Superhydrophobic, Superoleophobic and Lubricant Infused Slippery Behavior on Copper Oxide Nano-structured Substrates

PubMed Central

Ujjain, Sanjeev Kumar; Roy, Pritam Kumar; Kumar, Sumana; Singha, Subhash; Khare, Krishnacharya

2016-01-01

Alloys, specifically steel, are considered as the workhorse of our society and are inimitable engineering materials in the field of infrastructure, industry and possesses significant applications in our daily life. However, creating a robust synthetic metallic surface that repels various liquids has remained extremely challenging. The wettability of a solid surface is known to be governed by its geometric nano-/micro structure and the chemical composition. Here, we are demonstrating a facile and economical way to generate copper oxide micro-nano structures with spherical (0D), needle (1D) and hierarchical cauliflower (3D) morphologies on galvanized steel substrates using a simple chemical bath deposition method. These nano/micro textured steel surfaces, on subsequent coating of a low surface energy material display excellent superhydrophobic, superoleophobic and slippery behavior. Polydimethylsiloxane coated textured surfaces illustrate superhydrophobicity with water contact angle about 160°(2) and critical sliding angle ~2°. When functionalized with low-surface energy perfluoroalkylsilane, these surfaces display high repellency for low surface tension oils as well as hydrocarbons. Among them, the hierarchical cauliflower morphology exhibits re-entrant structure thereby showing the best superoleophobicity with contact angle 149° for dodecane. Once infused with a lubricant like silicone oil, they show excellent slippery behavior with low contact angle hysteresis (~ 2°) for water drops. PMID:27752098

Uniting Superhydrophobic, Superoleophobic and Lubricant Infused Slippery Behavior on Copper Oxide Nano-structured Substrates

NASA Astrophysics Data System (ADS)

Ujjain, Sanjeev Kumar; Roy, Pritam Kumar; Kumar, Sumana; Singha, Subhash; Khare, Krishnacharya

2016-10-01

Alloys, specifically steel, are considered as the workhorse of our society and are inimitable engineering materials in the field of infrastructure, industry and possesses significant applications in our daily life. However, creating a robust synthetic metallic surface that repels various liquids has remained extremely challenging. The wettability of a solid surface is known to be governed by its geometric nano-/micro structure and the chemical composition. Here, we are demonstrating a facile and economical way to generate copper oxide micro-nano structures with spherical (0D), needle (1D) and hierarchical cauliflower (3D) morphologies on galvanized steel substrates using a simple chemical bath deposition method. These nano/micro textured steel surfaces, on subsequent coating of a low surface energy material display excellent superhydrophobic, superoleophobic and slippery behavior. Polydimethylsiloxane coated textured surfaces illustrate superhydrophobicity with water contact angle about 160°(2) and critical sliding angle ~2°. When functionalized with low-surface energy perfluoroalkylsilane, these surfaces display high repellency for low surface tension oils as well as hydrocarbons. Among them, the hierarchical cauliflower morphology exhibits re-entrant structure thereby showing the best superoleophobicity with contact angle 149° for dodecane. Once infused with a lubricant like silicone oil, they show excellent slippery behavior with low contact angle hysteresis (~ 2°) for water drops.

An Efficient, Recyclable, and Stable Immobilized Biocatalyst Based on Bioinspired Microcapsules-in-Hydrogel Scaffolds.

PubMed

Zhang, Shaohua; Jiang, Zhongyi; Shi, Jiafu; Wang, Xueyan; Han, Pingping; Qian, Weilun

2016-09-28

Design and preparation of high-performance immobilized biocatalysts with exquisite structures and elucidation of their profound structure-performance relationship are highly desired for green and sustainable biotransformation processes. Learning from nature has been recognized as a shortcut to achieve such an impressive goal. Loose connective tissue, which is composed of hierarchically organized cells by extracellular matrix (ECM) and is recognized as an efficient catalytic system to ensure the ordered proceeding of metabolism, may offer an ideal prototype for preparing immobilized biocatalysts with high catalytic activity, recyclability, and stability. Inspired by the hierarchical structure of loose connective tissue, we prepared an immobilized biocatalyst enabled by microcapsules-in-hydrogel (MCH) scaffolds via biomimetic mineralization in agarose hydrogel. In brief, the in situ synthesized hybrid microcapsules encapsulated with glucose oxidase (GOD) are hierarchically organized by the fibrous framework of agarose hydrogel, where the fibers are intercalated into the capsule wall. The as-prepared immobilized biocatalyst shows structure-dependent catalytic performance. The porous hydrogel permits free diffusion of glucose molecules (diffusion coefficient: ∼6 × 10(-6) cm(2) s(-1), close to that in water) and retains the enzyme activity as much as possible after immobilization (initial reaction rate: 1.5 × 10(-2) mM min(-1)). The monolithic macroscale of agarose hydrogel facilitates the easy recycling of the immobilized biocatalyst (only by using tweezers), which contributes to the nonactivity decline during the recycling test. The fiber-intercalating structure elevates the mechanical stability of the in situ synthesized hybrid microcapsules, which inhibits the leaching and enhances the stability of the encapsulated GOD, achieving immobilization efficiency of ∼95%. This study will, therefore, provide a generic method for the hierarchical organization of (bio)active materials and the rational design of novel (bio)catalysts.

Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

PubMed Central

Leistenschneider, Desirée; Jäckel, Nicolas; Hippauf, Felix; Presser, Volker

2017-01-01

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g−1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g−1 in organic and 138 F g−1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g−1 in EMIM-BF4. PMID:28781699

Epitaxial Growth of Hetero-Ln-MOF Hierarchical Single Crystals for Domain- and Orientation-Controlled Multicolor Luminescence 3D Coding Capability.

PubMed

Pan, Mei; Zhu, Yi-Xuan; Wu, Kai; Chen, Ling; Hou, Ya-Jun; Yin, Shao-Yun; Wang, Hai-Ping; Fan, Ya-Nan; Su, Cheng-Yong

2017-11-13

Core-shell or striped heteroatomic lanthanide metal-organic framework hierarchical single crystals were obtained by liquid-phase anisotropic epitaxial growth, maintaining identical periodic organization while simultaneously exhibiting spatially segregated structure. Different types of domain and orientation-controlled multicolor photophysical models are presented, which show either visually distinguishable or visible/near infrared (NIR) emissive colors. This provides a new bottom-up strategy toward the design of hierarchical molecular systems, offering high-throughput and multiplexed luminescence color tunability and readability. The unique capability of combining spectroscopic coding with 3D (three-dimensional) microscale spatial coding is established, providing potential applications in anti-counterfeiting, color barcoding, and other types of integrated and miniaturized optoelectronic materials and devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on Desorption Process of n-Heptane and Methyl Cyclohexane Using UiO-66 with Hierarchical Pores.

PubMed

Chen, Sijia; Zhang, Lin; Zhang, Zhao; Qian, Gang; Liu, Zongjian; Cui, Qun; Wang, Haiyan

2018-06-06

UiO-66 (UiO for University of Oslo), is a zirconium-based MOF with reverse shape selectivity, gives an alternative way to produce high purity n-heptane used for the manufacture of high-purity pharmaceuticals. Couple of studies have shown that UiO-66 gives a high selectivity on the separation of n-/iso-alkanes. However, the microporous structure of UiO-66 causes poor mass transport during the desorption process. In this work, hierarchical-pore UiO-66 (H-UiO-66) was synthesized and utilized as an adsorbent of n-heptane (nHEP) and methyl cyclohexane (MCH) for systematically studying the desorption process of n/iso-alkanes. A suite of physical methods, including XRD patterns verified the UiO-66 structures and HRTEM showed the existence of hierarchical pores. N2 adsorption-desorption isotherms further confirmed the size distribution of hierarchical pores in H-UiO-66. Of particular note, the MCH/nHEP selectivity of H-UiO-66 is similar with UiO-66 in the same adsorption conditions, the desorption process of nHEP/MCH from H-UiO-66 is dramatically enhanced, viz, the desorption rates for nHEP/MCH from H-UiO-66 is enhanced by 30%/23% as comparing to UiO-66 at most. Moreover, desorption activation energy (Ed) derived from temperature-programmed desorption (TPD) experiments indicate that the Ed for nHEP/MCH is lower on H-UiO-66, i.e., the Ed of MCH on H-UiO-66 is ~37% lower than that on UiO-66 at most, leading to a milder condition for the desorption process. The introduction of hierarchical structures will be applicable for the optimization of desorption process during separation on porous materials.

Hierarchical structure and compressive deformation mechanisms of bighorn sheep (Ovis canadensis) horn.

PubMed

Huang, Wei; Zaheri, Alireza; Jung, Jae-Young; Espinosa, Horacio D; Mckittrick, Joanna

2017-12-01

Bighorn sheep (Ovis canadensis) rams hurl themselves at each other at speeds of ∼9 m/s (20 mph) to fight for dominance and mating rights. This necessitates impact resistance and energy absorption mechanisms, which stem from material-structure components in horns. In this study, the material hierarchical structure as well as correlations between the structure and mechanical properties are investigated. The major microstructural elements of horns are found as tubules and cell lamellae, which are oriented with (∼30⁰) angle with respect to each other. The cell lamellae contain keratin cells, in the shape of pancakes, possessing an average thickness of ∼2 µm and diameter of ∼20-30 µm. The morphology of keratin cells reveals the presence of keratin fibers and intermediate filaments with diameter of ∼200 nm and ∼12 nm, respectively, parallel to the cell surface. Quasi-static and high strain rate impact experiments, in different loading directions and hydration states, revealed a strong strain rate dependency for both dried and hydrated conditions. A strong anisotropy behavior was observed under impact for the dried state. The results show that the radial direction is the most preferable impact orientation because of its superior energy absorption. Detailed failure mechanisms under the aforementioned conditions are examined by bar impact recovery experiments. Shear banding, buckling of cell lamellae, and delamination in longitudinal and transverse direction were identified as the cause for strain softening under high strain rate impact. While collapse of tubules occurs in both quasi-static and impact tests, in radial and transverse directions, the former leads to more energy absorption and impact resistance. Bighorn sheep (Ovis canadensis) horns show remarkable impact resistance and energy absorption when undergoing high speed impact during the intraspecific fights. The present work illustrates the hierarchical structure of bighorn sheep horn at different length scales and investigates the energy dissipation mechanisms under different strain rates, loading orientations and hydration states. These results demonstrate how horn dissipates large amounts of energy, thus provide a new path to fabricate energy absorbent and crashworthiness engineering materials. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Fabrication of micro/nano hierarchical structures with analysis on the surface mechanics

NASA Astrophysics Data System (ADS)

Jheng, Yu-Sheng; Lee, Yeeu-Chang

2016-10-01

Biomimicry refers to the imitation of mechanisms and features found in living creatures using artificial methods. This study used optical lithography, colloidal lithography, and dry etching to mimic the micro/nano hierarchical structures covering the soles of gecko feet. We measured the static contact angle and contact angle hysteresis to reveal the behavior of liquid drops on the hierarchical structures. Pulling tests were also performed to measure the resistance of movement between the hierarchical structures and a testing plate. Our results reveal that hierarchical structures at the micro-/nano-scale are considerably hydrophobic, they provide good flow characteristics, and they generate more contact force than do surfaces with micro-scale cylindrical structures.

Room temperature synthesis and highly enhanced visible light photocatalytic activity of porous BiOI/BiOCl composites nanoplates microflowers.

PubMed

Dong, Fan; Sun, Yanjuan; Fu, Min; Wu, Zhongbiao; Lee, S C

2012-06-15

This research represents a highly enhanced visible light photocatalytic removal of 450 ppb level of nitric oxide (NO) in air by utilizing flower-like hierarchical porous BiOI/BiOCl composites synthesized by a room temperature template free method for the first time. The facile synthesis method avoids high temperature treatment, use of organic precursors and production of undesirable organic byproducts during synthesis process. The result indicated that the as-prepared BiOI/BiOCl composites samples were solid solution and were self-assembled hierarchically with single-crystal nanoplates. The aggregation of the self-assembled nanoplates resulted in the formation of 3D hierarchical porous architecture containing tri-model mesopores. The coupling to BiOI with BiOCl led to down-lowered valence band (VB) and up-lifted conduction band (CB) in contrast to BiOI, making the composites suitable for visible light excitation. The BiOI/BiOCl composites samples exhibited highly enhanced visible light photocatalytic activity for removal of NO in air due to the large surface areas and pore volume, hierarchical structure and modified band structure, exceeding that of P25, BiOI, C-doped TiO(2) and Bi(2)WO(6). This research results could provide a cost-effective approach for the synthesis of porous hierarchical materials and enhancement of photocatalyst performance for environmental and energetic applications owing to its low cost and easy scaling up. Copyright © 2012 Elsevier B.V. All rights reserved.

A hybrid phenomenological model for ferroelectroelastic ceramics. Part II: Morphotropic PZT ceramics

NASA Astrophysics Data System (ADS)

Stark, S.; Neumeister, P.; Balke, H.

2016-10-01

In this part II of a two part series, the rate-independent hybrid phenomenological constitutive model introduced in part I is modified to account for the material behavior of morphotropic lead zirconate titanate ceramics (PZT ceramics). The modifications are based on a discussion of the available literature results regarding the micro-structure of these materials. In particular, a monoclinic phase and a highly simplified representation of the hierarchical structure of micro-domains and nano-domains observed experimentally are incorporated into the model. It is shown that experimental data for the commercially available morphotropic PZT material PIC151 (PI Ceramic GmbH, Lederhose, Germany) can be reproduced and predicted based on the modified hybrid model.

Order from the disorder: hierarchical nanostructures self-assembled from the gas phase (Conference Presentation)

NASA Astrophysics Data System (ADS)

Di Fonzo, Fabio

2017-02-01

The assembly of nanoscale building blocks in engineered mesostructures is one of the fundamental goals of nanotechnology. Among the various processes developed to date, self-assembly emerges as one of the most promising, since it relays solely on basic physico-chemical forces. Our research is focused on a new type of self-assembly strategy from the gas-phase: Scattered Ballistic Deposition (SBD). SBD arises from the interaction of a supersonic molecular beam with a static gas and enables the growth of quasi-1D hierarchical mesostructures. Overall, they resemble a forest composed of individual, high aspect-ratio, tree-like structures, assembled from amorphous or crystalline nanoparticles. SBD is a general occurring phenomenon and can be obtained with different vapour or cluster sources. In particular, SBD by Pulsed Laser Deposition is a convenient physical vapor technique that allows the generation of supersonic plasma jets from any inorganic material irrespective of melting temperature, preserving even the most complex stoichiometries. One of the advantages of PLD over other vapour deposition techniques is extremely wide operational pressure range, from UHV to ambient pressure. These characteristics allowed us to develop quasi-1D hierarchical nanostructures from different transition metal oxides, semiconductors and metals. The precise control offered by the SBD-PLD technique over material properties at the nanoscale allowed us to fabricate ultra-thin, high efficiency hierarchical porous photonic crystals with Bragg reflectivity up to 85%. In this communication we will discuss the application of these materials to solar energy harvesting and storage, stimuli responsive photonic crystals and smart surfaces with digital control of their wettability behaviour.

Bioinspired Hierarchical Alumina-Graphene Oxide-Poly(vinyl alcohol) Artificial Nacre with Optimized Strength and Toughness.

PubMed

Wang, Jinrong; Qiao, Jinliang; Wang, Jianfeng; Zhu, Ying; Jiang, Lei

2015-05-06

Due to hierarchical organization of micro- and nanostructures, natural nacre exhibits extraordinary strength and toughness, and thus provides a superior model for the design and fabrication of high-performance artificial composite materials. Although great progress has been made in constructing layered composites by alternately stacking hard inorganic platelets and soft polymers, the real issue is that the excellent strength of these composites was obtained at the sacrifice of toughness. In this work, inspired by the layered aragonite microplatelets/chitin nanofibers-protein structure of natural nacre, alumina microplatelets-graphene oxide nanosheets-poly(vinyl alcohol) (Al2O3/GO-PVA) artificial nacre is successfully constructed through layer-by-layer bottom-up assembly, in which Al2O3 and GO-PVA act as "bricks" and "mortar", respectively. The artificial nacre has hierarchical "brick-and-mortar" structure and exhibits excellent strength (143 ± 13 MPa) and toughness (9.2 ± 2.7 MJ/m(3)), which are superior to those of natural nacre (80-135 MPa, 1.8 MJ/m(3)). It was demonstrated that the multiscale hierarchical structure of ultrathin GO nanosheets and submicrometer-thick Al2O3 platelets can deal with the conflict between strength and toughness, thus leading to the excellent mechanical properties that cannot be obtained using only one size of platelet. We strongly believe that the work presented here provides a creative strategy for designing and developing new composites with excellent strength and toughness.

Toughening mystery of natural rubber deciphered by double network incorporating hierarchical structures

PubMed Central

Zhou, Weiming; Li, Xiangyang; Lu, Jie; Huang, Ningdong; Chen, Liang; Qi, Zeming; Li, Liangbin; Liang, Haiyi

2014-01-01

As an indispensible material for modern society, natural rubber possesses peerless mechanical properties such as strength and toughness over its artificial analogues, which remains a mystery. Intensive experimental and theoretical investigations have revealed the self-enhancement of natural rubber due to strain-induced crystallization. However a rigorous model on the self-enhancement, elucidating natural rubber's extraordinary mechanical properties, is obscured by deficient understanding of the local hierarchical structure under strain. With spatially resolved synchrotron radiation micro-beam scanning X-ray diffraction we discover weak oscillation in distributions of strain-induced crystallinity around crack tip for stretched natural rubber film, demonstrating a soft-hard double network structure. The fracture energy enhancement factor obtained by utilizing the double network model indicates an enhancement of toughness by 3 orders. It's proposed that upon stretching spontaneously developed double network structures integrating hierarchy at multi length-scale in natural rubber play an essential role in its remarkable mechanical performance. PMID:25511479

A review of experimental techniques to produce a nacre-like structure.

PubMed

Corni, I; Harvey, T J; Wharton, J A; Stokes, K R; Walsh, F C; Wood, R J K

2012-09-01

The performance of man-made materials can be improved by exploring new structures inspired by the architecture of biological materials. Natural materials, such as nacre (mother-of-pearl), can have outstanding mechanical properties due to their complicated architecture and hierarchical structure at the nano-, micro- and meso-levels which have evolved over millions of years. This review describes the numerous experimental methods explored to date to produce composites with structures and mechanical properties similar to those of natural nacre. The materials produced have sizes ranging from nanometres to centimetres, processing times varying from a few minutes to several months and a different range of mechanical properties that render them suitable for various applications. For the first time, these techniques have been divided into those producing bulk materials, coatings and free-standing films. This is due to the fact that the material's application strongly depends on its dimensions and different results have been reported by applying the same technique to produce materials with different sizes. The limitations and capabilities of these methodologies have been also described.

Multi-Material Tissue Engineering Scaffold with Hierarchical Pore Architecture.

PubMed

Morgan, Kathy Ye; Sklaviadis, Demetra; Tochka, Zachary L; Fischer, Kristin M; Hearon, Keith; Morgan, Thomas D; Langer, Robert; Freed, Lisa E

2016-08-23

Multi-material polymer scaffolds with multiscale pore architectures were characterized and tested with vascular and heart cells as part of a platform for replacing damaged heart muscle. Vascular and muscle scaffolds were constructed from a new material, poly(limonene thioether) (PLT32i), which met the design criteria of slow biodegradability, elastomeric mechanical properties, and facile processing. The vascular-parenchymal interface was a poly(glycerol sebacate) (PGS) porous membrane that met different criteria of rapid biodegradability, high oxygen permeance, and high porosity. A hierarchical architecture of primary (macroscale) and secondary (microscale) pores was created by casting the PLT32i prepolymer onto sintered spheres of poly(methyl methacrylate) (PMMA) within precisely patterned molds followed by photocuring, de-molding, and leaching out the PMMA. Pre-fabricated polymer templates were cellularized, assembled, and perfused in order to engineer spatially organized, contractile heart tissue. Structural and functional analyses showed that the primary pores guided heart cell alignment and enabled robust perfusion while the secondary pores increased heart cell retention and reduced polymer volume fraction.

Carbon composition with hierarchical porosity, and methods of preparation

DOEpatents

Mayes, Richard T; Dai, Sheng

2014-10-21

A method for fabricating a porous carbon material possessing a hierarchical porosity, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic component, (iii) a dione component in which carbonyl groups are adjacent, and (iv) an acidic component, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a carbon material possessing a hierarchical porosity comprised of mesopores and macropores. Also described are the resulting hierarchical porous carbon material, a capacitive deionization device in which the porous carbon material is incorporated, as well as methods for desalinating water by use of said capacitive deionization device.

Polythiophene-block-poly(γ-benzyl L-glutamate): Synthesis and study of a new rod-rod block copolymer

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

Wu, Zong-Quan; Ono, Robert J.; Chen, Zheng

2011-01-01

Coupling of ethynyl terminated poly(3-hexylthiophene) with azide terminated poly(γ-benzyl L-glutamate) afforded the respective block copolymer in good yield and high purity; this material was found to self assemble into hierarchal structures in solution and in the solid state.

Synthesis of hollow silica spheres with hierarchical shell structure by the dual action of liquid indium microbeads in vapor-liquid-solid growth.

PubMed

Wang, Jian-Tao; Wang, Hui; Ou, Xue-Mei; Lee, Chun-Sing; Zhang, Xiao-Hong

2011-07-05

Geometry-based adhesion arising from hierarchical surface structure enables microspheres to adhere to cells strongly, which is essential for inorganic microcapsules that function as drug delivery or diagnostic imaging agents. However, constructing a hierarchical structure on the outer shell of the products via the current microcapsule synthesis method is difficult. This work presents a novel approach to fabricating hollow microspheres with a hierarchical shell structure through the vapor-liquid-solid (VLS) process in which liquid indium droplets act as both templates for the formation of silica capsules and catalysts for the growth of hierarchical shell structure. This hierarchical shell structure offers the hollow microsphere an enhanced geometry-based adhesion. The results provide a facile method for fabricating hollow spheres and enriching their function through tailoring the geometry of their outer shells. © 2011 American Chemical Society

Nanostructured core-shell electrode materials for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Jiang, Long-bo; Yuan, Xing-zhong; Liang, Jie; Zhang, Jin; Wang, Hou; Zeng, Guang-ming

2016-11-01

Core-shell nanostructure represents a unique system for applications in electrochemical energy storage devices. Owing to the unique characteristics featuring high power delivery and long-term cycling stability, electrochemical capacitors (ECs) have emerged as one of the most attractive electrochemical storage systems since they can complement or even replace batteries in the energy storage field, especially when high power delivery or uptake is needed. This review aims to summarize recent progress on core-shell nanostructures for advanced supercapacitor applications in view of their hierarchical architecture which not only create the desired hierarchical porous channels, but also possess higher electrical conductivity and better structural mechanical stability. The core-shell nanostructures include carbon/carbon, carbon/metal oxide, carbon/conducting polymer, metal oxide/metal oxide, metal oxide/conducting polymer, conducting polymer/conducting polymer, and even more complex ternary core-shell nanoparticles. The preparation strategies, electrochemical performances, and structural stabilities of core-shell materials for ECs are summarized. The relationship between core-shell nanostructure and electrochemical performance is discussed in detail. In addition, the challenges and new trends in core-shell nanomaterials development have also been proposed.

Supercapacitor electrode materials with hierarchically structured pores from carbonization of MWCNTs and ZIF-8 composites.

PubMed

Li, Xueqin; Hao, Changlong; Tang, Bochong; Wang, Yue; Liu, Mei; Wang, Yuanwei; Zhu, Yihua; Lu, Chenguang; Tang, Zhiyong

2017-02-09

Due to their high specific surface area and good electric conductivity, nitrogen-doped porous carbons (NPCs) and carbon nanotubes (CNTs) have attracted much attention for electrochemical energy storage applications. In the present work, we firstly prepared MWCNT/ZIF-8 composites by decoration of zeolitic imidazolate frameworks (ZIF-8) onto the surface of multi-walled CNTs (MWCNTs), then obtained MWCNT/NPCs by the direct carbonization of MWCNT/ZIF-8. By controlling the reaction conditions, MWCNT/ZIF-8 with three different particle sizes were synthesized. The effect of NPCs size on capacitance performance has been evaluated in detail. The MWCNT/NPC with large-sized NPC (MWCNT/NPC-L) displayed the highest specific capacitance of 293.4 F g -1 at the scan rate of 5 mV s -1 and only lost 4.2% of capacitance after 10 000 cyclic voltammetry cycles, which was attributed to the hierarchically structured pores, N-doping and high electrical conductivity. The studies of symmetric two-electrode supercapacitor cells also confirmed MWCNT/NPC-L as efficient electrode materials that have good electrochemical performance, especially for high-rate applications.

Self-assembled hierarchical nanostructures for high-efficiency porous photonic crystals.

PubMed

Passoni, Luca; Criante, Luigino; Fumagalli, Francesco; Scotognella, Francesco; Lanzani, Guglielmo; Di Fonzo, Fabio

2014-12-23

The nanoscale modulation of material properties such as porosity and morphology is used in the natural world to mold the flow of light and to obtain structural colors. The ability to mimic these strategies while adding technological functionality has the potential to open up a broad array of applications. Porous photonic crystals are one such technological candidate, but have typically underachieved in terms of available materials, structural and optical quality, compatibility with different substrates (e.g., silicon, flexible organics), and scalability. We report here an alternative fabrication method based on the bottom-up self-assembly of elementary building blocks from the gas phase into high surface area photonic hierarchical nanostructures at room temperature. Periodic refractive index modulation is achieved by stacking layers with different nanoarchitectures. High-efficiency porous Bragg reflectors are successfully fabricated with sub-micrometer thick films on glass, silicon, and flexible substrates. High diffraction efficiency broadband mirrors (R≈1), opto-fluidic switches, and arrays of photonic crystal pixels with size<10 μm are demonstrated. Possible applications in filtering, sensing, electro-optical modulation, solar cells, and photocatalysis are envisioned.

Construction of crystal structure prototype database: methods and applications.

PubMed

Su, Chuanxun; Lv, Jian; Li, Quan; Wang, Hui; Zhang, Lijun; Wang, Yanchao; Ma, Yanming

2017-04-26

Crystal structure prototype data have become a useful source of information for materials discovery in the fields of crystallography, chemistry, physics, and materials science. This work reports the development of a robust and efficient method for assessing the similarity of structures on the basis of their interatomic distances. Using this method, we proposed a simple and unambiguous definition of crystal structure prototype based on hierarchical clustering theory, and constructed the crystal structure prototype database (CSPD) by filtering the known crystallographic structures in a database. With similar method, a program structure prototype analysis package (SPAP) was developed to remove similar structures in CALYPSO prediction results and extract predicted low energy structures for a separate theoretical structure database. A series of statistics describing the distribution of crystal structure prototypes in the CSPD was compiled to provide an important insight for structure prediction and high-throughput calculations. Illustrative examples of the application of the proposed database are given, including the generation of initial structures for structure prediction and determination of the prototype structure in databases. These examples demonstrate the CSPD to be a generally applicable and useful tool for materials discovery.

Construction of crystal structure prototype database: methods and applications

NASA Astrophysics Data System (ADS)

Su, Chuanxun; Lv, Jian; Li, Quan; Wang, Hui; Zhang, Lijun; Wang, Yanchao; Ma, Yanming

2017-04-01

Crystal structure prototype data have become a useful source of information for materials discovery in the fields of crystallography, chemistry, physics, and materials science. This work reports the development of a robust and efficient method for assessing the similarity of structures on the basis of their interatomic distances. Using this method, we proposed a simple and unambiguous definition of crystal structure prototype based on hierarchical clustering theory, and constructed the crystal structure prototype database (CSPD) by filtering the known crystallographic structures in a database. With similar method, a program structure prototype analysis package (SPAP) was developed to remove similar structures in CALYPSO prediction results and extract predicted low energy structures for a separate theoretical structure database. A series of statistics describing the distribution of crystal structure prototypes in the CSPD was compiled to provide an important insight for structure prediction and high-throughput calculations. Illustrative examples of the application of the proposed database are given, including the generation of initial structures for structure prediction and determination of the prototype structure in databases. These examples demonstrate the CSPD to be a generally applicable and useful tool for materials discovery.

Supercapacitors: A Hierarchical Carbon Derived from Sponge-Templated Activation of Graphene Oxide for High-Performance Supercapacitor Electrodes (Adv. Mater. 26/2016).

PubMed

Xu, Jin; Tan, Ziqi; Zeng, Wencong; Chen, Guanxiong; Wu, Shuilin; Zhao, Yuan; Ni, Kun; Tao, Zhuchen; Ikram, Mujtaba; Ji, Hengxing; Zhu, Yanwu

2016-07-01

H. Ji, Y. Zhu, and co-workers demonstrate a 3D hierarchically porous carbon by introducing a polyurethane sponge to template graphene oxide into a 3D interconnected structure while KOH activation generates abundant micropores in its backbone. As described on page 5222, a supercapacitor assembled with this carbon material achieves a high energy density of 89 W h kg(-1) (64 W h L(-1) ) and outstanding power density due to its shortened ion transport distance in three dimensions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How hierarchical is language use?

PubMed Central

Frank, Stefan L.; Bod, Rens; Christiansen, Morten H.

2012-01-01

It is generally assumed that hierarchical phrase structure plays a central role in human language. However, considerations of simplicity and evolutionary continuity suggest that hierarchical structure should not be invoked too hastily. Indeed, recent neurophysiological, behavioural and computational studies show that sequential sentence structure has considerable explanatory power and that hierarchical processing is often not involved. In this paper, we review evidence from the recent literature supporting the hypothesis that sequential structure may be fundamental to the comprehension, production and acquisition of human language. Moreover, we provide a preliminary sketch outlining a non-hierarchical model of language use and discuss its implications and testable predictions. If linguistic phenomena can be explained by sequential rather than hierarchical structure, this will have considerable impact in a wide range of fields, such as linguistics, ethology, cognitive neuroscience, psychology and computer science. PMID:22977157

Super-elastic and fatigue resistant carbon material with lamellar multi-arch microstructure

NASA Astrophysics Data System (ADS)

Gao, Huai-Ling; Zhu, Yin-Bo; Mao, Li-Bo; Wang, Feng-Chao; Luo, Xi-Sheng; Liu, Yang-Yi; Lu, Yang; Pan, Zhao; Ge, Jin; Shen, Wei; Zheng, Ya-Rong; Xu, Liang; Wang, Lin-Jun; Xu, Wei-Hong; Wu, Heng-An; Yu, Shu-Hong

2016-09-01

Low-density compressible materials enable various applications but are often hindered by structure-derived fatigue failure, weak elasticity with slow recovery speed and large energy dissipation. Here we demonstrate a carbon material with microstructure-derived super-elasticity and high fatigue resistance achieved by designing a hierarchical lamellar architecture composed of thousands of microscale arches that serve as elastic units. The obtained monolithic carbon material can rebound a steel ball in spring-like fashion with fast recovery speed (~580 mm s-1), and demonstrates complete recovery and small energy dissipation (~0.2) in each compress-release cycle, even under 90% strain. Particularly, the material can maintain structural integrity after more than 106 cycles at 20% strain and 2.5 × 105 cycles at 50% strain. This structural material, although constructed using an intrinsically brittle carbon constituent, is simultaneously super-elastic, highly compressible and fatigue resistant to a degree even greater than that of previously reported compressible foams mainly made from more robust constituents.

Hierarchical nanostructures for functional materials.

PubMed

Qin, Zhao; Buehler, Markus J

2018-07-13

Naturally occurring biomaterials often have amazing functions, such as mechanical, thermal, electromagnetic, biological, optical and acoustic. These superior performances are often due to their hierarchical organizations of natural materials, starting from the nanoscopic scale and extending all the way to the macroscopic level. This topical issue features articles dedicated to understanding, designing and characterizing complex de novo hierarchical materials for a variety of applications. This research area is quickly evolving, and we hope that future work will drive the rational designs of innovative functional materials and generate deep impacts to broad engineering fields that address major societal challenges and needs.

Hierarchical nanostructures for functional materials

NASA Astrophysics Data System (ADS)

Qin, Zhao; Buehler, Markus J.

2018-07-01

Naturally occurring biomaterials often have amazing functions, such as mechanical, thermal, electromagnetic, biological, optical and acoustic. These superior performances are often due to their hierarchical organizations of natural materials, starting from the nanoscopic scale and extending all the way to the macroscopic level. This topical issue features articles dedicated to understanding, designing and characterizing complex de novo hierarchical materials for a variety of applications. This research area is quickly evolving, and we hope that future work will drive the rational designs of innovative functional materials and generate deep impacts to broad engineering fields that address major societal challenges and needs.

Scalable Preparation of Ternary Hierarchical Silicon Oxide-Nickel-Graphite Composites for Lithium-Ion Batteries

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

Wang , Jing; Bao, Wurigumula; Ma, Lu

2015-11-09

Silicon monoxide is a promising anode candidate because of its high theoretical capacity and good cycle performance. To solve the problems associated with this material, including large volume changes during charge-discharge processes, we report a ternary hierarchical silicon oxide–nickel–graphite composite prepared by a facile two-step ball-milling method. The composite consists of nano-Si dispersed silicon oxides embedded in nano-Ni/graphite matrices (Si@SiOx/Ni/graphite). In the composite, crystalline nano-Si particles are generated by the mechanochemical reduction of SiO by ball milling with Ni. These nano-Si dispersed oxides have abundant electrochemical activity and can provide high Li-ion storage capacity. Furthermore, the milled nano-Ni/graphite matrices stickmore » well to active materials and interconnect to form a crosslinked framework, which functions as an electrical highway and a mechanical backbone so that all silicon oxide particles become electrochemically active. Owing to these advanced structural and electrochemical characteristics, the composite enhances the utilization efficiency of SiO, accommodates its large volume expansion upon cycling, and has good ionic and electronic conductivity. The composite electrodes thus exhibit substantial improvements in electrochemical performance. This ternary hierarchical Si@SiOx/Ni/graphite composite is a promising candidate anode material for high-energy lithium-ion batteries. Additionally, the mechanochemical ball-milling method is low cost and easy to reproduce, indicating potential for the commercial production of the composite materials.« less

Scalable Preparation of Ternary Hierarchical Silicon Oxide-Nickel-Graphite Composites for Lithium-Ion Batteries.

PubMed

Wang, Jing; Bao, Wurigumula; Ma, Lu; Tan, Guoqiang; Su, Yuefeng; Chen, Shi; Wu, Feng; Lu, Jun; Amine, Khalil

2015-12-07

Silicon monoxide is a promising anode candidate because of its high theoretical capacity and good cycle performance. To solve the problems associated with this material, including large volume changes during charge-discharge processes, we report a ternary hierarchical silicon oxide-nickel-graphite composite prepared by a facile two-step ball-milling method. The composite consists of nano-Si dispersed silicon oxides embedded in nano-Ni/graphite matrices (Si@SiOx /Ni/graphite). In the composite, crystalline nano-Si particles are generated by the mechanochemical reduction of SiO by ball milling with Ni. These nano-Si dispersed oxides have abundant electrochemical activity and can provide high Li-ion storage capacity. Furthermore, the milled nano-Ni/graphite matrices stick well to active materials and interconnect to form a crosslinked framework, which functions as an electrical highway and a mechanical backbone so that all silicon oxide particles become electrochemically active. Owing to these advanced structural and electrochemical characteristics, the composite enhances the utilization efficiency of SiO, accommodates its large volume expansion upon cycling, and has good ionic and electronic conductivity. The composite electrodes thus exhibit substantial improvements in electrochemical performance. This ternary hierarchical Si@SiOx /Ni/graphite composite is a promising candidate anode material for high-energy lithium-ion batteries. Additionally, the mechanochemical ball-milling method is low cost and easy to reproduce, indicating potential for the commercial production of the composite materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How protein materials balance strength, robustness, and adaptability

PubMed Central

Buehler, Markus J.; Yung, Yu Ching

2010-01-01

Proteins form the basis of a wide range of biological materials such as hair, skin, bone, spider silk, or cells, which play an important role in providing key functions to biological systems. The focus of this article is to discuss how protein materials are capable of balancing multiple, seemingly incompatible properties such as strength, robustness, and adaptability. To illustrate this, we review bottom-up materiomics studies focused on the mechanical behavior of protein materials at multiple scales, from nano to macro. We focus on alpha-helix based intermediate filament proteins as a model system to explain why the utilization of hierarchical structural features is vital to their ability to combine strength, robustness, and adaptability. Experimental studies demonstrating the activation of angiogenesis, the growth of new blood vessels, are presented as an example of how adaptability of structure in biological tissue is achieved through changes in gene expression that result in an altered material structure. We analyze the concepts in light of the universality and diversity of the structural makeup of protein materials and discuss the findings in the context of potential fundamental evolutionary principles that control their nanoscale structure. We conclude with a discussion of multiscale science in biology and de novo materials design. PMID:20676305

High-performance supercapacitor and lithium-ion battery based on 3D hierarchical NH4F-induced nickel cobaltate nanosheet-nanowire cluster arrays as self-supported electrodes.

PubMed

Chen, Yuejiao; Qu, Baihua; Hu, Lingling; Xu, Zhi; Li, Qiuhong; Wang, Taihong

2013-10-21

A facile hydrothermal method is developed for large-scale production of three-dimensional (3D) hierarchical porous nickel cobaltate nanowire cluster arrays derived from nanosheet arrays with robust adhesion on Ni foam. Based on the morphology evolution upon reaction time, a possible formation process is proposed. The role of NH4F in formation of the structure has also been investigated based on different NH4F amounts. This unique structure significantly enhances the electroactive surface areas of the NiCo2O4 arrays, leading to better interfacial/chemical distributions at the nanoscale, fast ion and electron transfer and good strain accommodation. Thus, when it is used for supercapacitor testing, a specific capacitance of 1069 F g(-1) at a very high current density of 100 A g(-1) was obtained. Even after more than 10,000 cycles at various large current densities, a capacitance of 2000 F g(-1) at 10 A g(-1) with 93.8% retention can be achieved. It also exhibits a high-power density (26.1 kW kg(-1)) at a discharge current density of 80 A g(-1). When used as an anode material for lithium-ion batteries (LIBs), it presents a high reversible capacity of 976 mA h g(-1) at a rate of 200 mA g(-1) with good cycling stability and rate capability. This array material is rarely used as an anode material. Our results show that this unique 3D hierarchical porous nickel cobaltite is promising for electrochemical energy applications.

Ultralight mesoporous magnetic frameworks by interfacial assembly of Prussian blue nanocubes.

PubMed

Kong, Biao; Tang, Jing; Wu, Zhangxiong; Wei, Jing; Wu, Hao; Wang, Yongcheng; Zheng, Gengfeng; Zhao, Dongyuan

2014-03-10

A facile approach for the synthesis of ultralight iron oxide hierarchical structures with tailorable macro- and mesoporosity is reported. This method entails the growth of porous Prussian blue (PB) single crystals on the surface of a polyurethane sponge, followed by in situ thermal conversion of PB crystals into three-dimensional mesoporous iron oxide (3DMI) architectures. Compared to previously reported ultralight materials, the 3DMI architectures possess hierarchical macro- and mesoporous frameworks with multiple advantageous features, including high surface area (ca. 117 m(2) g(-1)) and ultralow density (6-11 mg cm(-3)). Furthermore, they can be synthesized on a kilogram scale. More importantly, these 3DMI structures exhibit superparamagnetism and tunable hydrophilicity/hydrophobicity, thus allowing for efficient multiphase interfacial adsorption and fast multiphase catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Effectively Activated Hierarchical Nano-/Microspherical Li 1.2 Ni 0.2 Mn 0.6 O 2 Cathode for Long-Life and High-Rate Lithium-Ion Batteries

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

Li, Yu; Bai, Ying; Bi, Xuanxuan

2016-03-04

Rechargeable lithium-ion batteries with high energy and high power density are required in the application of electric vehicles and portable electronics. Herein, we introduce a type of spherical Li-rich cathode material, Li1.2Ni0.2Mn0.6O2, assembled from uniform nanocubes by a facile polyvinylpyrrolidone (PVP)-assisted hydrothermal method. The material with a hierarchical nano-/microstructure exhibits stable high-rate performance. Furthermore, the precipitant (i.e., urea) and the structure-directing agent (i.e., PVP) effectively activated the Li2MnO3 components in the microscale material to achieve a high specific capacity of 298.5 mAh g-1 in the first cycle. This Li-rich cathode material still delivered 243 mAh g-1 at 0.1 C aftermore » 200 cycles and the capacity retentions at 0.5, 1, 2, and 5mC were 94.4, 78.7, 76.3, and 67.8 % after 150 cycles, respectively. The results make this Li-rich nano-/microstructure a promising cathode material for long-life and high-performance lithium-ion batteries.« less

Hierarchically organized behavior and its neural foundations: A reinforcement-learning perspective

PubMed Central

Botvinick, Matthew M.; Niv, Yael; Barto, Andrew C.

2009-01-01

Research on human and animal behavior has long emphasized its hierarchical structure — the divisibility of ongoing behavior into discrete tasks, which are comprised of subtask sequences, which in turn are built of simple actions. The hierarchical structure of behavior has also been of enduring interest within neuroscience, where it has been widely considered to reflect prefrontal cortical functions. In this paper, we reexamine behavioral hierarchy and its neural substrates from the point of view of recent developments in computational reinforcement learning. Specifically, we consider a set of approaches known collectively as hierarchical reinforcement learning, which extend the reinforcement learning paradigm by allowing the learning agent to aggregate actions into reusable subroutines or skills. A close look at the components of hierarchical reinforcement learning suggests how they might map onto neural structures, in particular regions within the dorsolateral and orbital prefrontal cortex. It also suggests specific ways in which hierarchical reinforcement learning might provide a complement to existing psychological models of hierarchically structured behavior. A particularly important question that hierarchical reinforcement learning brings to the fore is that of how learning identifies new action routines that are likely to provide useful building blocks in solving a wide range of future problems. Here and at many other points, hierarchical reinforcement learning offers an appealing framework for investigating the computational and neural underpinnings of hierarchically structured behavior. PMID:18926527

Construction of hierarchically porous metal–organic frameworks through linker labilization

DOE PAGES

Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; ...

2017-05-25

One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragmentsmore » by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.« less

Bio-derived three-dimensional hierarchical carbon-graphene-TiO2 as electrode for supercapacitors.

PubMed

Jiang, Lili; Ren, Zhifeng; Chen, Shuo; Zhang, Qinyong; Lu, Xiong; Zhang, Hongping; Wan, Guojiang

2018-03-13

This paper reports a novel loofah-derived hierarchical scaffold to obtain three-dimensional biocarbon-graphene-TiO 2 (BC-G-TiO 2 ) composite materials as electrodes for supercapacitors. The loofah scaffold was first loaded with G and TiO 2 by immersing, squeezing, and loosening into the mixed solution of graphene oxide and titania, and then carbonized at 900 °C to form the BC-G-TiO 2 composite. The synergistic effects of the naturally hierarchical biocarbon structure, graphene, and TiO 2 nanoparticles on the electrochemical properties are analyzed. The biocarbon provides a high interconnection and an easy accessibility surface for the electrolyte. Graphene bridged the BC and TiO 2 nanoparticles, improved the conductivity of the BC-G-TiO 2 composite, and increased the electron transfer efficiency. TiO 2 nanoparticles also contributed to the pesudocapacitance and electrochemical stability.

Cobalt silicate hierarchical hollow spheres for lithium-ion batteries.

PubMed

Yang, Jun; Guo, Yuanyuan; Zhang, Yufei; Sun, Chencheng; Yan, Qingyu; Dong, Xiaochen

2016-09-09

In this paper, the synthesis of cobalt silicate novel hierarchical hollow spheres via a facile hydrothermal method is presented. With a unique hollow structure, the Co2SiO4 provides a large surface area, which can shorten the lithium ions diffusion length and effectively accommodate the volumetic variation during the lithiation/de-lithiation process. Serving as an anode material in lithium-ion battery application, the Co2SiO4 electrode demonstrates a high reversible specific capacity (first-cycle charge capacity of 948.6 mAh g(-1) at 100 mA g(-1)), a cycling durability (specific capacity of 791.4 mAh g(-1) after 100 cycles at 100 mA g(-1)), and a good rate capability (specific capacity of 349.4 mAh g(-1) at 10 A g(-1)). The results indicate that the cobalt silicate hierarchical hollow sphere holds the potential applications in energy storage electrodes.

Facile synthesis of uniform hierarchical composites CuO-CeO2 for enhanced dye removal

NASA Astrophysics Data System (ADS)

Xu, Pan; Niu, Helin; Chen, Jingshuai; Song, Jiming; Mao, Changjie; Zhang, Shengyi; Gao, Yuanhao; Chen, Changle

2016-12-01

The hierarchically shaped CuO-CeO2 composites were prepared through a facile solvothermal method without using any template. The as-prepared products were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and N2 adsorption-desorption analysis. In the characterization, we found that CuO-CeO2 composites were showed uniform size and morphology which were consisted of the secondary nanoflakes interconnected with each other. Most interestingly, the composites showed efficient performance to remove methyl blue and Congo red dyes from water with maximum adsorption capacities of 2131.24 and 1072.09 mg g-1, respectively. In addition, because of their larger surface area and the unique hierarchical structures, the adsorption performance of the CuO-CeO2 composites is much better than the materials of CuO and CeO2.

Construction of hierarchically porous metal-organic frameworks through linker labilization

NASA Astrophysics Data System (ADS)

Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai

2017-05-01

A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

Thermal Instability Induced Oriented 2D Pores for Enhanced Sodium Storage.

PubMed

Kong, Lingjun; Xie, Chen-Chao; Gu, Haichen; Wang, Chao-Peng; Zhou, Xianlong; Liu, Jian; Zhou, Zhen; Li, Zhao-Yang; Zhu, Jian; Bu, Xian-He

2018-04-19

Hierarchical porous structures are highly desired for various applications. However, it is still challenging to obtain such materials with tunable architectures. Here, this paper reports hierarchical nanomaterials with oriented 2D pores by taking advantages of thermally instable bonds in vanadium-based metal-organic frameworks (MOFs). High-temperature calcination of these MOFs accompanied by the loss of coordinated water molecules and other components enables the formation of orderly slit-like 2D pores in vanadium oxide/porous carbon nanorods (VO x /PCs). This unique combination leads to an increase of the reactive surface area. In addition, optimized VO x /PCs demonstrate high-rate capability and ultralong cycling life for sodium storage. The assembled full cells also show high capacity and cycling stability. This report provides an effective strategy for producing MOFs-derived composites with hierarchical porous architectures for energy storage. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-Archimedean reaction-ultradiffusion equations and complex hierarchic systems

NASA Astrophysics Data System (ADS)

Zúñiga-Galindo, W. A.

2018-06-01

We initiate the study of non-Archimedean reaction-ultradiffusion equations and their connections with models of complex hierarchic systems. From a mathematical perspective, the equations studied here are the p-adic counterpart of the integro-differential models for phase separation introduced by Bates and Chmaj. Our equations are also generalizations of the ultradiffusion equations on trees studied in the 1980s by Ogielski, Stein, Bachas, Huberman, among others, and also generalizations of the master equations of the Avetisov et al models, which describe certain complex hierarchic systems. From a physical perspective, our equations are gradient flows of non-Archimedean free energy functionals and their solutions describe the macroscopic density profile of a bistable material whose space of states has an ultrametric structure. Some of our results are p-adic analogs of some well-known results in the Archimedean setting, however, the mechanism of diffusion is completely different due to the fact that it occurs in an ultrametric space.

Role of local assembly in the hierarchical crystallization of associating colloidal hard hemispheres

NASA Astrophysics Data System (ADS)

Lei, Qun-li; Hadinoto, Kunn; Ni, Ran

2017-10-01

Hierarchical self-assembly consisting of local associations of simple building blocks for the formation of complex structures widely exists in nature, while the essential role of local assembly remains unknown. In this work, by using computer simulations, we study a simple model system consisting of associating colloidal hemispheres crystallizing into face-centered-cubic crystals comprised of spherical dimers of hemispheres, focusing on the effect of dimer formation on the hierarchical crystallization. We found that besides assisting the crystal nucleation because of increasing the symmetry of building blocks, the association between hemispheres can also induce both reentrant melting and reentrant crystallization depending on the range of interaction. Especially when the interaction is highly sticky, we observe a novel reentrant crystallization of identical crystals, which melt only in a certain temperature range. This offers another axis in fabricating responsive crystalline materials by tuning the fluctuation of local association.

Polymeric surfaces exhibiting photocatalytic activity and controlled anisotropic wettability

NASA Astrophysics Data System (ADS)

Anastasiadis, Spiros H.; Frysali, Melani A.; Papoutsakis, Lampros; Kenanakis, George; Stratakis, Emmanuel; Vamvakaki, Maria; Mountrichas, Grigoris; Pispas, Stergios

2015-03-01

In this work we focus on surfaces, which exhibit controlled, switchable wettability in response to one or more external stimuli as well as photocatalytic activity. For this we are inspired from nature to produce surfaces with a dual-scale hierarchical roughness and combine them with the appropriate inorganic and/or polymer coating. The combination of the hierarchical surface with a ZnO coating and a pH- or temperature-responsive polymer results in efficient photo-active properties as well as reversible superhydrophobic / superhydrophilic surfaces. Furthermore, we fabricate surfaces with unidirectional wettability variation. Overall, such complex surfaces require advanced design, combining hierarchically structured surfaces with suitable polymeric materials. Acknowledgment: This research was partially supported by the European Union (European Social Fund, ESF) and Greek national funds through the ``ARISTEIA II'' Action (SMART-SURF) of the Operational Programme ``Education and Lifelong Learning,'' NSRF 2007-2013, via the General Secretariat for Research & Technology, Ministry of Education and Religious Affairs, Greece.

Construction of hierarchically porous metal–organic frameworks through linker labilization

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

Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng

One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragmentsmore » by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.« less

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides.

PubMed

Jood, Priyanka; Ohta, Michihiro

2015-03-16

Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS₂-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS₂ sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor.

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides

PubMed Central

Jood, Priyanka; Ohta, Michihiro

2015-01-01

Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS2-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS2 sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor. PMID:28787992

Hierarchical porous structured zeolite composite for removal of ionic contaminants from waste streams and effective encapsulation of hazardous waste.

PubMed

Al-Jubouri, Sama M; Curry, Nicholas A; Holmes, Stuart M

2016-12-15

A hierarchical structured composite made from clinoptilolite supported on date stones carbon is synthesized using two techniques. The composites are manufactured by fixing a natural zeolite (clinoptilolite) to the porous surface of date stones carbon or by direct hydrothermal synthesis on to the surface to provide a supported high surface area ion-exchange material for metal ion removal from aqueous streams. The fixing of the clinoptilolite is achieved using sucrose and citric acid as a binder. The composites and pure clinoptilolite were compared to test the efficacy for the removal of Sr 2+ ions from an aqueous phase. The encapsulation of the Sr 2+ using either vitrification or a geo-polymer addition was tested to ensure that the hazardous waste can be made safe for disposal. The hierarchical structured composites were shown to achieve a higher ion exchange capacity per gram of zeolite than the pure clinoptilolite (65mg/g for the pure natural clinoptilolite and 72mg/g for the pure synthesized clinoptilolite) with the synthesized composite (160mg/g) having higher capacity than the natural clinoptilolite composite (95mg/g). The rate at which the equilibria were established followed the same trend showing the composite structure facilitates diffusion to the ion-exchange sites in the zeolite. Copyright © 2016 Elsevier B.V. All rights reserved.

Overview of Biomineralization and Nanobacteria

NASA Technical Reports Server (NTRS)

Ciftcioglu, N.; McKay, D. S.

2005-01-01

Biomineralization is a frequently used term in nanotechnology, astrobiology, geology, and medicine. In the process of biomineralization, a living organism provides a chemical environment that controls the nucleation and growth of unique mineral phases. Often these materials exhibit hierarchical structural order, leading to superior physical properties, not found either in their inorganic counterparts or in synthetic materials. Biomineralization is widespread in the biosphere and hundreds of different minerals are produced or assisted by a variety of organisms from bacteria to humans. Teeth, bones, kidney stones, and skeletons of algae, mussels, and magnetotactic bacteria are all examples of biomineralization. We do not fully understand the control mechanism of biomineralization either in primitive or in developed organisms. The presence of organic molecules, among other characteristics, can influence the coherence length for X-ray scattering in biogenic crystals. Control over biomineral properties can be accomplished at a myriad of levels, including the regulation of particle size, shape, crystal orientation, polymorphic structure, defect texture, and particle assembly. In the latter case, cellular processes enable control in both the spatial and temporal domain in such a way that hierarchical composite structures can be built which increase the toughness and durability of the material, which is invaluable for load-bearing materials such as bones, teeth, mollusk shells, etc. Durability of biominerals produces remarkably preserved bacterial and cyanobacterial microfossils from billions of years-old samples. The differentiation between microfossils and nonbiogenic artifacts has been a lively discussion subject in astrobiology especially in the last decade. Clearly, more detailed information on the mechanism of biomineralization, and the effect of organic matter on crystal formation/fossilization would help focus such discussions.

Hierarchical nonlinear behavior of hot composite structures

NASA Technical Reports Server (NTRS)

Murthy, P. L. N.; Chamis, C. C.; Singhal, S. N.

1993-01-01

Hierarchical computational procedures are described to simulate the multiple scale thermal/mechanical behavior of high temperature metal matrix composites (HT-MMC) in the following three broad areas: (1) behavior of HT-MMC's from micromechanics to laminate via METCAN (Metal Matrix Composite Analyzer), (2) tailoring of HT-MMC behavior for optimum specific performance via MMLT (Metal Matrix Laminate Tailoring), and (3) HT-MMC structural response for hot structural components via HITCAN (High Temperature Composite Analyzer). Representative results from each area are presented to illustrate the effectiveness of computational simulation procedures and accompanying computer codes. The sample case results show that METCAN can be used to simulate material behavior such as the entire creep span; MMLT can be used to concurrently tailor the fabrication process and the interphase layer for optimum performance such as minimum residual stresses; and HITCAN can be used to predict the structural behavior such as the deformed shape due to component fabrication. These codes constitute virtual portable desk-top test laboratories for characterizing HT-MMC laminates, tailoring the fabrication process, and qualifying structural components made from them.

Syntactic Structure and Artificial Grammar Learning: The Learnability of Embedded Hierarchical Structures

ERIC Educational Resources Information Center

de Vries, Meinou H.; Monaghan, Padraic; Knecht, Stefan; Zwitserlood, Pienie

2008-01-01

Embedded hierarchical structures, such as "the rat the cat ate was brown", constitute a core generative property of a natural language theory. Several recent studies have reported learning of hierarchical embeddings in artificial grammar learning (AGL) tasks, and described the functional specificity of Broca's area for processing such structures.…

Materials by Design—A Perspective From Atoms to Structures

PubMed Central

Buehler, Markus J.

2013-01-01

Biological materials are effectively synthesized, controlled, and used for a variety of purposes—in spite of limitations in energy, quality, and quantity of their building blocks. Whereas the chemical composition of materials in the living world plays a some role in achieving functional properties, the way components are connected at different length scales defines what material properties can be achieved, how they can be altered to meet functional requirements, and how they fail in disease states and other extreme conditions. Recent work has demonstrated this by using large-scale computer simulations to predict materials properties from fundamental molecular principles, combined with experimental work and new mathematical techniques to categorize complex structure-property relationships into a systematic framework. Enabled by such categorization, we discuss opportunities based on the exploitation of concepts from distinct hierarchical systems that share common principles in how function is created, linking music to materials science. PMID:24163499

Versatile Micromechanics Model for Multiscale Analysis of Composite Structures

NASA Astrophysics Data System (ADS)

Kwon, Y. W.; Park, M. S.

2013-08-01

A general-purpose micromechanics model was developed so that the model could be applied to various composite materials such as reinforced by particles, long fibers and short fibers as well as those containing micro voids. Additionally, the model can be used with hierarchical composite materials. The micromechanics model can be used to compute effective material properties like elastic moduli, shear moduli, Poisson's ratios, and coefficients of thermal expansion for the various composite materials. The model can also calculate the strains and stresses at the constituent material level such as fibers, particles, and whiskers from the composite level stresses and strains. The model was implemented into ABAQUS using the UMAT option for multiscale analysis. An extensive set of examples are presented to demonstrate the reliability and accuracy of the developed micromechanics model for different kinds of composite materials. Another set of examples is provided to study the multiscale analysis of composite structures.

Fast-pulverization enabled simultaneous enhancement on cycling stability and rate capability of C@NiFe2O4 hierarchical fibrous bundle

NASA Astrophysics Data System (ADS)

Chen, Zerui; Zhang, Yu; Wang, Xiaoling; Sun, Wenping; Dou, Shixue; Huang, Xin; Shi, Bi

2017-09-01

Electrochemical-grinding induced pulverization is the origin of capacity fading in NiFe2O4. Increasing current density normally accelerates the pulverization that deteriorates lithium storage properties of NiFe2O4. Here we show that the high current induced fast-pulverization can serve as an efficient activation strategy for quick and simultaneous enhancement on cycling stability and rate capability of NiFe2O4 nanoparticles (NPs) that are densely packed on the hierarchically structured carbon nanofiber strand. At a high current density, the pulverization of NiFe2O4 NPs can be accomplished in a few cycles exposing more active surface. During the fast-pulverization, the hierarchically structured carbon nanofiber strand maintains conductive contact for the densely packed NiFe2O4 NPs regardless of charge or discharge, which also effectively suppresses the repetitive breaks and growths of solid-electrolyte-interphase (SEI) via multiple-level structural adaption that favourites the quick formation of a thin and dense SEI, thus providing strong interparticle connectivity with enhancement on cycling stability and rate capability (e.g. doubled capacity). Our findings demonstrate the potential importance of high current induced fast-pulverization as an efficient activation strategy for achieving durable electrode materials suffering from electrochemical-grinding effects.

High Mass Loading MnO2 with Hierarchical Nanostructures for Supercapacitors.

PubMed

Huang, Zi-Hang; Song, Yu; Feng, Dong-Yang; Sun, Zhen; Sun, Xiaoqi; Liu, Xiao-Xia

2018-04-24

Metal oxides have attracted renewed interest as promising electrode materials for high energy density supercapacitors. However, the electrochemical performance of metal oxide materials deteriorates significantly with the increase of mass loading due to their moderate electronic and ionic conductivities. This limits their practical energy. Herein, we perform a morphology and phase-controlled electrodeposition of MnO 2 with ultrahigh mass loading of 10 mg cm -2 on a carbon cloth substrate to achieve high overall capacitance without sacrificing the electrochemical performance. Under optimum conditions, a hierarchical nanostructured architecture was constructed by interconnection of primary two-dimensional ε-MnO 2 nanosheets and secondary one-dimensional α-MnO 2 nanorod arrays. The specific hetero-nanostructures ensure facile ionic and electric transport in the entire electrode and maintain the structure stability during cycling. The hierarchically structured MnO 2 electrode with high mass loading yields an outstanding areal capacitance of 3.04 F cm -2 (or a specific capacitance of 304 F g -1 ) at 3 mA cm -2 and an excellent rate capability comparable to those of low mass loading MnO 2 electrodes. Finally, the aqueous and all-solid asymmetric supercapacitors (ASCs) assembled with our MnO 2 cathode exhibit extremely high volumetric energy densities (8.3 mWh cm -3 at the power density of 0.28 W cm -3 for aqueous ASC and 8.0 mWh cm -3 at 0.65 W cm -3 for all-solid ASC), superior to most state-of-the-art supercapacitors.

Hierarchical Heterostructures of NiCo2O4@XMoO4 (X = Ni, Co) as an Electrode Material for High-Performance Supercapacitors.

PubMed

Hu, Jiyu; Qian, Feng; Song, Guosheng; Wang, Linlin

2016-12-01

Hierarchical heterostructures of NiCo2O4@XMoO4 (X = Ni, Co) were developed as an electrode material for supercapacitor with improved pseudocapacitive performance. Within these hierarchical heterostructures, the mesoporous NiCo2O4 nanosheet arrays directly grown on the Ni foam can not only act as an excellent pseudocapacitive material but also serve as a hierarchical scaffold for growing NiMoO4 or CoMoO4 electroactive materials (nanosheets). The electrode made of NiCo2O4@NiMoO4 presented a highest areal capacitance of 3.74 F/cm(2) at 2 mA/cm(2), which was much higher than the electrodes made of NiCo2O4@CoMoO4 (2.452 F/cm(2)) and NiCo2O4 (0.456 F/cm(2)), respectively. Meanwhile, the NiCo2O4@NiMoO4 electrode exhibited good rate capability. It suggested the potential of the hierarchical heterostructures of NiCo2O4@CoMoO4 as an electrode material in supercapacitors.

Metal oxide nanostructures with hierarchical morphology

DOEpatents

Ren, Zhifeng; Lao, Jing Yu; Banerjee, Debasish

2007-11-13

The present invention relates generally to metal oxide materials with varied symmetrical nanostructure morphologies. In particular, the present invention provides metal oxide materials comprising one or more metallic oxides with three-dimensionally ordered nanostructural morphologies, including hierarchical morphologies. The present invention also provides methods for producing such metal oxide materials.

Hierarchical thermoelectrics: crystal grain boundaries as scalable phonon scatterers

NASA Astrophysics Data System (ADS)

Selli, Daniele; Boulfelfel, Salah Eddine; Schapotschnikow, Philipp; Donadio, Davide; Leoni, Stefano

2016-02-01

Thermoelectric materials are strategically valuable for sustainable development, as they allow for the generation of electrical energy from wasted heat. In recent years several strategies have demonstrated some efficiency in improving thermoelectric properties. Dopants affect carrier concentration, while thermal conductivity can be influenced by alloying and nanostructuring. Features at the nanoscale positively contribute to scattering phonons, however those with long mean free paths remain difficult to alter. Here we use the concept of hierarchical nano-grains to demonstrate thermal conductivity reduction in rocksalt lead chalcogenides. We demonstrate that grains can be obtained by taking advantage of the reconstructions along the phase transition path that connects the rocksalt structure to its high-pressure form. Since grain features naturally change as a function of size, they impact thermal conductivity over different length scales. To understand this effect we use a combination of advanced molecular dynamics techniques to engineer grains and to evaluate thermal conductivity in PbSe. By affecting grain morphologies only, i.e. at constant chemistry, two distinct effects emerge: the lattice thermal conductivity is significantly lowered with respect to the perfect crystal, and its temperature dependence is markedly suppressed. This is due to an increased scattering of low-frequency phonons by grain boundaries over different size scales. Along this line we propose a viable process to produce hierarchical thermoelectric materials by applying pressure via a mechanical load or a shockwave as a novel paradigm for material design.

Coral-Inspired Nanoengineering Design for Long-Cycle and Flexible Lithium-Ion Battery Anode.

PubMed

Sun, Yangyong; Wang, Cheng; Xue, Yinghui; Zhang, Qin; Mendes, Rafael G; Chen, Linfeng; Zhang, Tao; Gemming, Thomas; Rümmeli, Mark H; Ai, Xinping; Fu, Lei

2016-04-13

Conversion reaction electrode materials (CREMs) have gained significant interest in lithium-ion batteries (LIBs) owing to their high theoretical gravimetric capacity. However, traditional CREMs-based electrodes, with large strain arising from Li(+) intercalation/deintercalation causes pulverization or electrical breakdown and cracking of the active materials which leads to structural collapse, limiting performance. Therefore, in order to construct electrodes with a strong tolerance to the strain incurred during the conversion reaction process, we design a coral-like three-dimensional (3D) hierarchical heterostructure by using cross-linked nanoflakes interspersed with nanoparticles (NPs) standing vertically on graphene foam (GF). The coral-like 3D hierarchical heterostructures can efficiently disperse the strain from both internal and external forces as well as increase the specific surface area for enhanced electrochemical reactions. These features lead to long-cycle stability and excellent flexibility in LIBs. Fe3O4 NPs and CoO NFs are utilized as a model system to demonstrate our strategy. The as-prepared coral-like hierarchical electrode is studied as an anode in LIBs for the first time and is shown to deliver a high reversible specific gravimetric capacity of ∼1200 mA h g(-1) at a rate of 0.5 A g(-1) for 400 cycles. In addition, our batteries can even power a green light-emitting diode when bent to high degrees confirming the excellent flexibility of the material.

Self-assembly of novel hierarchical flowers-like Sn3O4 decorated on 2D graphene nanosheets hybrid as high-performance anode materials for LIBs

NASA Astrophysics Data System (ADS)

Chen, Xuefang; Huang, Ying; Li, Tianpeng; Wei, Chao; Yan, Jing; Feng, Xuansheng

2017-05-01

Novel hierarchical flower-like Sn3O4 assembled by thin Sn3O4 nanosheets, as a kind of mixed-valence tin oxide, decorated on two-dimensional graphene nanosheets has been synthesized via a hydrothermal route and a step solution deoxidization technique. More importantly, as the anode materials for lithium ion batteries, the flower-like Sn3O4/graphene composite has not been investigated in detail. Noticeably, the nanosheets stemming from flower-like Sn3O4 and graphene have been linked together to form a specials three dimensional structure, possessing high active surface area and large enough inner spaces, which is benefit to the diffusion of liquid electrolyte into the electrode materials. In addition, the special structure could provide sufficient free volume to buffer the volume expansion appeared in the process of discharging and charging. The as-prepared flowers-like Sn3O4/graphene displayed excellent electrochemical performance with high capacity and good cycling stability as anode materials for lithium ion batteries. The discharge capacity is 1727 mAh/g in the first cycle at the current density of 60 mA/g. The obtained reversible capacity is 631mAh/g with a coulomb efficiency of 97.04% after 50 cycles. With its better electrochemical properties, the as-prepared flowers-like Sn3O4/graphene has the potential to be the next generation materials as an environmentally benign, abundant, cheap anode materials for lithium ion batteries.

Hierarchical Li1.2 Ni0.2 Mn0.6 O2 nanoplates with exposed {010} planes as high-performance cathode material for lithium-ion batteries.

PubMed

Chen, Lai; Su, Yuefeng; Chen, Shi; Li, Ning; Bao, Liying; Li, Weikang; Wang, Zhao; Wang, Meng; Wu, Feng

2014-10-22

Hierarchical Li1.2 Ni0.2 Mn0.6 O2 nanoplates with exposed {010} planes are designed and synthesized. In combination with the advantages from the hierarchical archi-tecture and the exposed electrochemically active {010} planes of layered materials, this material satisfies both efficient ion and electron transport and thus shows superior rate capability and excellent cycling stability. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-dimensional distribution of polymorphs and magnesium in a calcified underwater attachment system by diffraction tomography

PubMed Central

Leemreize, Hanna; Almer, Jonathan D.; Stock, Stuart R.; Birkedal, Henrik

2013-01-01

Biological materials display complicated three-dimensional hierarchical structures. Determining these structures is essential in understanding the link between material design and properties. Herein, we show how diffraction tomography can be used to determine the relative placement of the calcium carbonate polymorphs calcite and aragonite in the highly mineralized holdfast system of the bivalve Anomia simplex. In addition to high fidelity and non-destructive mapping of polymorphs, we use detailed analysis of X-ray diffraction peak positions in reconstructed powder diffraction data to determine the local degree of Mg substitution in the calcite phase. These data show how diffraction tomography can provide detailed multi-length scale information on complex materials in general and of biomineralized tissues in particular. PMID:23804437

Hierarchical Material Properties in Finite Element Analysis: The Oilfield Infrastructure Problem.

NASA Astrophysics Data System (ADS)

Weiss, C. J.; Wilson, G. A.

2017-12-01

Geophysical simulation of low-frequency electromagnetic signals within built environments such as urban centers and industrial landscapes facilities is a challenging computational problem because strong conductors (e.g., pipes, fences, rail lines, rebar, etc.) are not only highly conductive and/or magnetic relative to the surrounding geology, but they are very small in one or more of their physical length coordinates. Realistic modeling of such structures as idealized conductors has long been the standard approach; however this strategy carries with it computational burdens such as cumbersome implementation of internal boundary conditions, and limited flexibility for accommodating realistic geometries. Another standard approach is "brute force" discretization (often coupled with an equivalent medium model) whereby 100's of millions of voxels are used to represent these strong conductors, but at the cost of extreme computation times (and mesh design) for a simulation result when possible. To minimize these burdens, a new finite element scheme (Weiss, Geophysics, 2017) has been developed in which the material properties reside on a hierarchy of geometric simplicies (i.e., edges, facets and volumes) within an unstructured tetrahedral mesh. This allows thin sheet—like structures, such as subsurface fractures, to be economically represented by a connected set of triangular facets, for example, that freely conform to arbitrary "real world" geometries. The same holds thin pipe/wire-like structures, such as casings or pipelines. The hierarchical finite element scheme has been applied to problems in electro- and magnetostatics for oilfield problems where the elevated, but finite, conductivity and permeability of the steel-cased oil wells must be properly accounted for, yielding results that are otherwise unobtainable, with run times as low as a few 10s of seconds. Extension of the hierarchical finite element concept to broadband electromagnetics is presently underway, as are its implications for geophysical inversion.

Hierarchically porous Li3VO4/C nanocomposite as an advanced anode material for high-performance lithium-ion capacitors

NASA Astrophysics Data System (ADS)

Xu, Xuena; Niu, Feier; Zhang, Dapeng; Chu, Chenxiao; Wang, Chunsheng; Yang, Jian; Qian, Yitai

2018-04-01

Lithium-ion capacitors, as a hybrid electrochemical energy storage device, realize high specific energy and power density within one device, thus attracting extensive attention. Here, hierarchically porous Li3VO4/C nanocomposite is prepared by a solvo-thermal reaction, followed with a post-annealing process. This composite has macropores at the center and mesopores in the wall, thus effectively promoting electrolyte penetration and structure stability upon cycling simultaneously. Compared to mesoporous Li3VO4, the enhanced rate capability and specific capacity of hierarchically porous Li3VO4/C indicate the synergistic effect of mesopores and macropores. Inspired by these results, this composite is coupled with mesoporous carbon (CMK-3) for lithium-ion capacitors, generating a specific energy density of 105 Wh kg-1 at a power density of 188 W kg-1. Even if the power density increases to 9.3 kW kg-1, the energy density still remains 62 Wh kg-1. All these results demonstrate the promising potential of hierarchically porous Li3VO4 in lithium ion capacitors.

Three-Dimensional Honeycomb-Like Porous Carbon with Both Interconnected Hierarchical Porosity and Nitrogen Self-Doping from Cotton Seed Husk for Supercapacitor Electrode.

PubMed

Chen, Hui; Wang, Gang; Chen, Long; Dai, Bin; Yu, Feng

2018-06-08

Hierarchical porous structures with surface nitrogen-doped porous carbon are current research topics of interest for high performance supercapacitor electrode materials. Herein, a three-dimensional (3D) honeycomb-like porous carbon with interconnected hierarchical porosity and nitrogen self-doping was synthesized by simple and cost-efficient one-step KOH activation from waste cottonseed husk (a-CSHs). The obtained a-CSHs possessed hierarchical micro-, meso-, and macro-pores, a high specific surface area of 1694.1 m²/g, 3D architecture, and abundant self N-doping. Owing to these distinct features, a-CSHs delivered high specific capacitances of 238 F/g and 200 F/g at current densities of 0.5 A/g and 20 A/g, respectively, in a 6 mol/L KOH electrolyte, demonstrating good capacitance retention of 84%. The assembled a-CSHs-based symmetric supercapacitor also displayed high specific capacitance of 52 F/g at 0.5 A/g, with an energy density of 10.4 Wh/Kg at 300 W/Kg, and 91% capacitance retention after 5000 cycles at 10 A/g.

Hierarchical NiO-SiO2 composite hollow microspheres with enhanced adsorption affinity towards Congo red in water.

PubMed

Lei, Chunsheng; Zhu, Xiaofeng; Zhu, Bicheng; Yu, Jiaguo; Ho, Wingkei

2016-03-15

Hollow microspheres and hierarchical porous nanostructured materials with desired morphologies have gained remarkable attention for their potential applications in environmental technology. In this study, NiO-SiO2 hollow microspheres were prepared by co-precipitation with SiO2 and nickel salt as precursors, followed by dipping in alkaline solution and calcination. The samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, nitrogen adsorption, and X-ray photoelectron spectroscopy. The synthesized hollow spheres were composed of a SiO2 shell and hierarchical porous NiO nanosheets on the surface. Adsorption experiments suggested that NiO-SiO2 composite particles were powerful adsorbents for removal of Congo red from water, with a maximum adsorption capacity of 204.1 mg/g. The high specific surface areas, hollow structures, and hierarchical porous surfaces of the hollow composite particles are suitable for various applications, including adsorption of pollutants, chemical separation, and water purification. Copyright © 2015 Elsevier Inc. All rights reserved.

Generation of hierarchical pore systems in the titanosilicate ETS-10 by hydrogen peroxide treatment under microwave irradiation.

PubMed

Pavel, Claudiu C; Schmidt, Wolfgang

2006-02-28

Supermicropores and well-defined mesopores with an average size of 10 nm were created in ETS-10 structure by post-synthesis treatment with H2O2 under microwave irradiation. Macropores were also formed and the external surface area of the material was increased during the treatment.

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

Yusufoglu, Yusuf

Nature offers many exciting ideas and inspiration for the development of new materials and processes. The toughness of spider silk, the strength and lightweight of bone, and the adhesion abilities of the gecko's feet are some of the many examples of highperformance natural materials, which have attracted the interest of scientist to duplicate their properties in man-made materials. Materials found in nature combine many inspiring properties such as miniaturization, sophistication, hierarchical organization, hybridization, and adaptability. In all biological systems, whether very basic or highly complex, nature provides a multiplicity of materials, architectures, systems and functions. Generally, the architectural configurations andmore » material characteristics are the important features that have been duplicated from nature for building synthetic structural composites.« less

Construction of Hierarchical CuO/Cu₂O@NiCo₂S₄ Nanowire Arrays on Copper Foam for High Performance Supercapacitor Electrodes.

PubMed

Zhou, Luoxiao; He, Ying; Jia, Congpu; Pavlinek, Vladimir; Saha, Petr; Cheng, Qilin

2017-09-15

Hierarchical copper oxide @ ternary nickel cobalt sulfide (CuO/Cu₂O@NiCo₂S₄) core-shell nanowire arrays on Cu foam have been successfully constructed by a facile two-step strategy. Vertically aligned CuO/Cu₂O nanowire arrays are firstly grown on Cu foam by one-step thermal oxidation of Cu foam, followed by electrodeposition of NiCo₂S₄ nanosheets on the surface of CuO/Cu₂O nanowires to form the CuO/Cu₂O@NiCo₂S₄ core-shell nanostructures. Structural and morphological characterizations indicate that the average thickness of the NiCo₂S₄ nanosheets is ~20 nm and the diameter of CuO/Cu₂O core is ~50 nm. Electrochemical properties of the hierarchical composites as integrated binder-free electrodes for supercapacitor were evaluated by various electrochemical methods. The hierarchical composite electrodes could achieve ultrahigh specific capacitance of 3.186 F cm -2 at 10 mA cm -2 , good rate capability (82.06% capacitance retention at the current density from 2 to 50 mA cm -2 ) and excellent cycling stability, with capacitance retention of 96.73% after 2000 cycles at 10 mA cm -2 . These results demonstrate the significance of optimized design and fabrication of electrode materials with more sufficient electrolyte-electrode interface, robust structural integrity and fast ion/electron transfer.

Hierarchical honeycomb auxetic metamaterials

NASA Astrophysics Data System (ADS)

Mousanezhad, Davood; Babaee, Sahab; Ebrahimi, Hamid; Ghosh, Ranajay; Hamouda, Abdelmagid Salem; Bertoldi, Katia; Vaziri, Ashkan

2015-12-01

Most conventional materials expand in transverse directions when they are compressed uniaxially resulting in the familiar positive Poisson’s ratio. Here we develop a new class of two dimensional (2D) metamaterials with negative Poisson’s ratio that contract in transverse directions under uniaxial compressive loads leading to auxeticity. This is achieved through mechanical instabilities (i.e., buckling) introduced by structural hierarchy and retained over a wide range of applied compression. This unusual behavior is demonstrated experimentally and analyzed computationally. The work provides new insights into the role of structural organization and hierarchy in designing 2D auxetic metamaterials, and new opportunities for developing energy absorbing materials, tunable membrane filters, and acoustic dampeners.

Bioinspired Wood Nanotechnology for Functional Materials.

PubMed

Berglund, Lars A; Burgert, Ingo

2018-05-01

It is a challenging task to realize the vision of hierarchically structured nanomaterials for large-scale applications. Herein, the biomaterial wood as a large-scale biotemplate for functionalization at multiple scales is discussed, to provide an increased property range to this renewable and CO 2 -storing bioresource, which is available at low cost and in large quantities. The Progress Report reviews the emerging field of functional wood materials in view of the specific features of the structural template and novel nanotechnological approaches for the development of wood-polymer composites and wood-mineral hybrids for advanced property profiles and new functions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cauliflower-derived porous carbon without activation for electrochemical capacitor and CO2 capture applications

NASA Astrophysics Data System (ADS)

Du, Juan; Yu, Yifeng; Lv, Haijun; Chen, Chunlin; Zhang, Jian; Chen, Aibing

2018-01-01

Carbon materials have attracted great attention in CO2 capture and energy storage due to their excellent characteristics such as tunable pore structure, modulated surface properties and superior bulk conductivities, etc. Biomass, provided by nature with non-toxic, widespread, abundant, and sustainable advantages, is considered to be a very promising precursor of carbons for the view of economic, environmental, and societal issues. However, the preparation of high-performance biomass-derived carbons is still a big challenge because of the multistep process for their synthesis and subsequent activation. Herein, hierarchically porous structured carbon materials have been prepared by directly carbonizing dried cauliflowers without any addition of agents and activation process, featuring with large specific surface area, hierarchically porous structure and improved pore volume, as well as suitable nitrogen content. Being used as a solid-state CO2 adsorbent, the obtained product exhibited a high CO2 adsorption capacity of 3.1 mmol g-1 under 1 bar and 25 °C and a remarkable reusability of 96.7% retention after 20 adsorption/regeneration cycles. Our study reveals that choosing a good biomass source was significant as the unique structure of precursor endows the carbonized product with abundant pores without the need of any post-treatment. Used as an electrode material in electrochemical capacitor, the non-activated porous carbon displayed a fairly high specific capacitance of 228.9 F g-1 at 0.5 A g-1 and an outstanding stability of 99.2% retention after 5000 cycles at 5 A g-1. [Figure not available: see fulltext.

Recent advances of basic materials to obtain electrospun polymeric nanofibers for medical applications

NASA Astrophysics Data System (ADS)

Manea, L. R.; Hristian, L.; Leon, A. L.; Popa, A.

2016-08-01

The most important applications of electrospun polymeric nanofibers are by far those from biomedical field. From the biological point of view, almost all the human tissues and organs consist of nanofibroas structures. The examples include the bone, dentine, cartilage, tendons and skin. All these are characterized through different fibrous structures, hierarchically organized at nanometer scale. Electrospinning represents one of the nanotechnologies that permit to obtain such structures for cell cultures, besides other technologies, such as selfassembling and phase separation technologies. The basic materials used to produce electrospun nanofibers can be natural or synthetic, having polymeric, ceramic or composite nature. These materials are selected depending of the nature and structure of the tissue meant to be regenerated, namely: for the regeneration of smooth tissues regeneration one needs to process through electrospinning polymeric basic materials, while in order to obtain the supports for the regeneration of hard tissues one must mainly use ceramic materials or composite structures that permit imbedding the bioactive substances in distinctive zones of the matrix. This work presents recent studies concerning basic materials used to obtain electrospun polymeric nanofibers, and real possibilities to produce and implement these nanofibers in medical bioengineering applications.

Hierarchical columnar silicon anode structures for high energy density lithium sulfur batteries

NASA Astrophysics Data System (ADS)

Piwko, Markus; Kuntze, Thomas; Winkler, Sebastian; Straach, Steffen; Härtel, Paul; Althues, Holger; Kaskel, Stefan

2017-05-01

Silicon is a promising anode material for next generation lithium secondary batteries. To significantly increase the energy density of state of the art batteries with silicon, new concepts have to be developed and electrode structuring will become a key technology. Structuring is essential to reduce the macroscopic and microscopic electrode deformation, caused by the volume change during cycling. We report pulsed laser structuring for the generation of hierarchical columnar silicon films with outstanding high areal capacities up to 7.5 mAh cm-2 and good capacity retention. Unstructured columnar electrodes form a micron-sized block structure during the first cycle to compensate the volume expansion leading to macroscopic electrode deformation. At increased silicon loading, without additional structuring, pronounced distortion and the formation of cracks through the current collector causes cell failure. Pulsed laser ablation instead is demonstrated to avoid macroscopic electrode deformation by initial formation of the block structure. A full cell with lithiated silicon versus a carbon-sulfur cathode is assembled with only 15% overbalanced anode and low electrolyte amount (8 μl mgsulfur-1). While the capacity retention over 50 cycles is identical to a cell with high excess lithium anode, the volumetric energy density could be increased by 30%.

Super-hierarchical porous carbons derived from mixed biomass wastes by a stepwise removal strategy for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Peng, Lin; Liang, Yeru; Dong, Hanwu; Hu, Hang; Zhao, Xiao; Cai, Yijing; Xiao, Yong; Liu, Yingliang; Zheng, Mingtao

2018-02-01

The synthesis and energy storage application of hierarchical porous carbons with size ranging from nano-to micrometres has attracted considerable attention all over the world. Exploring eco-friendly and reliable synthesis of hierarchical porous carbons for supercapacitors with high energy density and high power is still of ongoing challenge. In this work, we report the design and synthesis of super-hierarchical porous carbons with highly developed porosity by a stepwise removal strategy for high-rate supercapacitors. The mixed biomass wastes of coconut shell and sewage sludge are employed as raw material. The as-prepared super-hierarchical porous carbons present high surface areas (3003 m2 g-1), large pore volume (2.04 cm3 g-1), appropriate porosity, and outstanding electrochemical performance. The dependence of electrochemical performance on structural, textural, and functional properties of carbons engineered by various synthesis strategies is investigated in detail. Moreover, the as-assembled symmetrical supercapacitor exhibits high energy density of 25.4 Wh kg-1 at a power density of 225 W kg-1 and retains 20.7 Wh kg-1 even at a very high power of 9000 W kg-1. This work provides an environmentally benign strategy and new insights to efficiently regulate the porosity of hierarchical porous carbons derived from biomass wastes for energy storage applications.

Exploiting Photo-induced Reactions in Polymer Blends to Create Hierarchically Ordered, Defect-free Materials

ScienceCinema

Balazs, Anna [University of Pittsburgh, Pittsburgh, Pennsylvania, United States

2017-12-09

Computer simulations reveal how photo-induced chemical reactions can be exploited to create long-range order in binary and ternary polymeric materials. The process is initiated by shining a spatially uniform light over a photosensitive AB binary blend, which undergoes both a reversible chemical reaction and phase separation. We then introduce a well-collimated, higher-intensity light source. Rastering this secondary light over the sample locally increases the reaction rate and causes formation of defect-free, spatially periodic structures. These binary structures resemble either the lamellar or hexagonal phases of microphase-separated di-block copolymers. We measure the regularity of the ordered structures as a function of the relative reaction rates for different values of the rastering speed and determine the optimal conditions for creating defect-free structures in the binary systems. We then add a non-reactive homo-polymer C, which is immiscible with both A and B. We show that this component migrates to regions that are illuminated by the secondary, higher-intensity light, allowing us to effectively write a pattern of C onto the AB film. Rastering over the ternary blend with this collimated light now leads to hierarchically ordered patterns of A, B, and C. The findings point to a facile, non-intrusive process for manufacturing high-quality polymeric devices in a low-cost, efficient manner.

Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO2 Adsorption.

PubMed

Chen, Chong; Li, Bingxue; Zhou, Lijin; Xia, Zefeng; Feng, Nengjie; Ding, Jing; Wang, Lei; Wan, Hui; Guan, Guofeng

2017-07-12

The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N 2 adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO 2 -TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO 2 on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO 2 uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO 2 adsorption indicated the stronger interactions between the surfaces and CO 2 molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO 2 adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO 2 adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.

Probing the structure of heterogeneous diluted materials by diffraction tomography.

PubMed

Bleuet, Pierre; Welcomme, Eléonore; Dooryhée, Eric; Susini, Jean; Hodeau, Jean-Louis; Walter, Philippe

2008-06-01

The advent of nanosciences calls for the development of local structural probes, in particular to characterize ill-ordered or heterogeneous materials. Furthermore, because materials properties are often related to their heterogeneity and the hierarchical arrangement of their structure, different structural probes covering a wide range of scales are required. X-ray diffraction is one of the prime structural methods but suffers from a relatively poor detection limit, whereas transmission electron analysis involves destructive sample preparation. Here we show the potential of coupling pencil-beam tomography with X-ray diffraction to examine unidentified phases in nanomaterials and polycrystalline materials. The demonstration is carried out on a high-pressure pellet containing several carbon phases and on a heterogeneous powder containing chalcedony and iron pigments. The present method enables a non-invasive structural refinement with a weight sensitivity of one part per thousand. It enables the extraction of the scattering patterns of amorphous and crystalline compounds with similar atomic densities and compositions. Furthermore, such a diffraction-tomography experiment can be carried out simultaneously with X-ray fluorescence, Compton and absorption tomographies, enabling a multimodal analysis of prime importance in materials science, chemistry, geology, environmental science, medical science, palaeontology and cultural heritage.

High Efficient Photo-Fenton Catalyst of α-Fe2O3/MoS2 Hierarchical Nanoheterostructures: Reutilization for Supercapacitors

NASA Astrophysics Data System (ADS)

Yang, Xijia; Sun, Haiming; Zhang, Lishu; Zhao, Lijun; Lian, Jianshe; Jiang, Qing

2016-08-01

A novel three-dimensional (3D) α-Fe2O3/MoS2 hierarchical nanoheterostructure is effectively synthesized via a facile hydrothermal method. The zero-dimensional (0D) Fe2O3 nanoparticles guide the growth of two-dimensional (2D) MoS2 nanosheets and formed 3D flower-like structures, while MoS2 facilitates the good dispersion of porous Fe2O3 with abundant oxygen vacancies. This charming 3D-structure with perfect match of non-equal dimension exhibits high recyclable photo-Fenton catalytic activity for Methyl orange pollutant and nice specific capacity in reusing as supercapacitor after catalysis. The synergistic effect between Fe2O3 and MoS2, the intermediate nanointerfaces, the 3D porous structures, and the abundant oxygen vacancies both contribute to highly active catalysis, nice electrochemical performance and stable cycling. This strategy is simple, cheap, and feasible for maximizing the value of the materials, as well as eliminating the secondary pollution.

High Efficient Photo-Fenton Catalyst of α-Fe2O3/MoS2 Hierarchical Nanoheterostructures: Reutilization for Supercapacitors.

PubMed

Yang, Xijia; Sun, Haiming; Zhang, Lishu; Zhao, Lijun; Lian, Jianshe; Jiang, Qing

2016-08-16

A novel three-dimensional (3D) α-Fe2O3/MoS2 hierarchical nanoheterostructure is effectively synthesized via a facile hydrothermal method. The zero-dimensional (0D) Fe2O3 nanoparticles guide the growth of two-dimensional (2D) MoS2 nanosheets and formed 3D flower-like structures, while MoS2 facilitates the good dispersion of porous Fe2O3 with abundant oxygen vacancies. This charming 3D-structure with perfect match of non-equal dimension exhibits high recyclable photo-Fenton catalytic activity for Methyl orange pollutant and nice specific capacity in reusing as supercapacitor after catalysis. The synergistic effect between Fe2O3 and MoS2, the intermediate nanointerfaces, the 3D porous structures, and the abundant oxygen vacancies both contribute to highly active catalysis, nice electrochemical performance and stable cycling. This strategy is simple, cheap, and feasible for maximizing the value of the materials, as well as eliminating the secondary pollution.

A frogspawn-inspired hierarchical porous NaTi2(PO4)3-C array for high-rate and long-life aqueous rechargeable sodium batteries

NASA Astrophysics Data System (ADS)

Zhao, Baidan; Lin, Bo; Zhang, Sen; Deng, Chao

2015-11-01

Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in a hierarchical porous array, which exhibits superior mechanical strength and high-efficiency oxygen permeability. It can be used as a model for designing a new high-performance electrode material, which has advantages such as a high surface area, fast mass transport and superior durability. Herein, we report a frogspawn-like NaTi2(PO4)3/C array prepared by a facile preform impregnation strategy. The framework is formed by a hollow carbon sphere connected by the NaTi2(PO4)3/C skeleton, and its hollow is filled with the NaTi2(PO4)3 nanospheres. The whole hierarchical porous three-dimensional array copies the structure of a frogspawn. This unique structure not only enables easy electrolyte percolation and fast electron/ion transport, but also enhances the reversible capacity and cycling durability. When it is applied as an anode of the aqueous sodium ion battery, it exhibits favorable high rate capability and superior cycling stability, and retains 89% of the initial capacity after two thousand cycles at 20 C. Moreover, the full cell using the frogspawn-inspired NaTi2(PO4)3-C as the anode and Na0.44MnO2 as the cathode is capable of ultralong cycling up to one thousand cycles at alternate 10 and 60 C, which is among the best of state-of-the-art aqueous sodium ion systems. Therefore, the frogspawn-inspired architecture provides a new strategy to the tailored design of polyanion materials for high-power applications.Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in a hierarchical porous array, which exhibits superior mechanical strength and high-efficiency oxygen permeability. It can be used as a model for designing a new high-performance electrode material, which has advantages such as a high surface area, fast mass transport and superior durability. Herein, we report a frogspawn-like NaTi2(PO4)3/C array prepared by a facile preform impregnation strategy. The framework is formed by a hollow carbon sphere connected by the NaTi2(PO4)3/C skeleton, and its hollow is filled with the NaTi2(PO4)3 nanospheres. The whole hierarchical porous three-dimensional array copies the structure of a frogspawn. This unique structure not only enables easy electrolyte percolation and fast electron/ion transport, but also enhances the reversible capacity and cycling durability. When it is applied as an anode of the aqueous sodium ion battery, it exhibits favorable high rate capability and superior cycling stability, and retains 89% of the initial capacity after two thousand cycles at 20 C. Moreover, the full cell using the frogspawn-inspired NaTi2(PO4)3-C as the anode and Na0.44MnO2 as the cathode is capable of ultralong cycling up to one thousand cycles at alternate 10 and 60 C, which is among the best of state-of-the-art aqueous sodium ion systems. Therefore, the frogspawn-inspired architecture provides a new strategy to the tailored design of polyanion materials for high-power applications. Electronic supplementary information (ESI) available: Lab-assembled preform impregnation system; EDX spectroscopy of the residual carbon matrix after HF treatment; atomic parameters and lattice parameters of the prepared array; crystal structural, morphological and physical characteristics of the reference samples, comparison of the electrochemical performance between the frogspawn-inspired array and the previously reported results. See DOI: 10.1039/c5nr06505d

An effective immunization strategy for airborne epidemics in modular and hierarchical social contact network

NASA Astrophysics Data System (ADS)

Song, Zhichao; Ge, Yuanzheng; Luo, Lei; Duan, Hong; Qiu, Xiaogang

2015-12-01

Social contact between individuals is the chief factor for airborne epidemic transmission among the crowd. Social contact networks, which describe the contact relationships among individuals, always exhibit overlapping qualities of communities, hierarchical structure and spatial-correlated. We find that traditional global targeted immunization strategy would lose its superiority in controlling the epidemic propagation in the social contact networks with modular and hierarchical structure. Therefore, we propose a hierarchical targeted immunization strategy to settle this problem. In this novel strategy, importance of the hierarchical structure is considered. Transmission control experiments of influenza H1N1 are carried out based on a modular and hierarchical network model. Results obtained indicate that hierarchical structure of the network is more critical than the degrees of the immunized targets and the modular network layer is the most important for the epidemic propagation control. Finally, the efficacy and stability of this novel immunization strategy have been validated as well.

Resolution of Singularities Introduced by Hierarchical Structure in Deep Neural Networks.

PubMed

Nitta, Tohru

2017-10-01

We present a theoretical analysis of singular points of artificial deep neural networks, resulting in providing deep neural network models having no critical points introduced by a hierarchical structure. It is considered that such deep neural network models have good nature for gradient-based optimization. First, we show that there exist a large number of critical points introduced by a hierarchical structure in deep neural networks as straight lines, depending on the number of hidden layers and the number of hidden neurons. Second, we derive a sufficient condition for deep neural networks having no critical points introduced by a hierarchical structure, which can be applied to general deep neural networks. It is also shown that the existence of critical points introduced by a hierarchical structure is determined by the rank and the regularity of weight matrices for a specific class of deep neural networks. Finally, two kinds of implementation methods of the sufficient conditions to have no critical points are provided. One is a learning algorithm that can avoid critical points introduced by the hierarchical structure during learning (called avoidant learning algorithm). The other is a neural network that does not have some critical points introduced by the hierarchical structure as an inherent property (called avoidant neural network).

Molecular-Level Design of Hierarchically Porous Carbons Codoped with Nitrogen and Phosphorus Capable of In Situ Self-Activation for Sustainable Energy Systems.

PubMed

Ai, Wei; Wang, Xuewan; Zou, Chenji; Du, Zhuzhu; Fan, Zhanxi; Zhang, Hua; Chen, Peng; Yu, Ting; Huang, Wei

2017-02-01

Hierarchically porous carbons are attracting tremendous attention in sustainable energy systems, such as lithium ion battery (LIB) and fuel cell, due to their excellent transport properties that arise from the high surface area and rich porosity. The state-of-the-art approaches for synthesizing hierarchically porous carbons normally require chemical- and/or template-assisted activation techniques, which is complicate, time consuming, and not feasible for large scale production. Here, a molecular-level design principle toward large-scale synthesis of nitrogen and phosphorus codoped hierarchically porous carbon (NPHPC) through an in situ self-activation process is proposed. The material is fabricated based on the direct pyrolysis of a well-designed polymer, melamine polyphosphate, which is capable of in situ self-activation to generate large specific surface area (1479 m 2 g -1 ) and hierarchical pores in the final NPHPC. As an anode material for LIB, NPHPC delivers a high reversible capacity of 1073 mAh g -1 and an excellent cyclic stability for 300 cycles with negligible capacity decay. The peculiar structural properties and synergistic effect of N and P codopants also enable NPHPC a promising electrocatalyst for oxygen reduction reaction, a key cathodic reaction process of many energy conversion devices (for example, fuel cells and metal air batteries). Electrochemical measurements show NPHPC a comparable electrocatalytic performance to commercial Pt/C catalyst (onset potential of 0.88 V vs reversible hydrogen electrode in alkaline medium) with excellent stability (89.8% retention after 20 000 s continuous operation) and superior methanol tolerance. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Basic characteristics and realization of production system control

NASA Astrophysics Data System (ADS)

Cheng, Shaopeng; Shell, Richard; Hall, Ernest L.

1992-11-01

This paper analyzes the issues involved in developing an intelligent production control system. It describes the basic characteristics of a production control system and an effective design methodology to realize the production control functions. Petri net, subsystem and hierarchical control concepts are applied to a computer integrated material handling system (MHS). Some communication and interface requirements of the MHS are also considered in this paper. The control system solution is illustrated with an actual MHS operation case which indicates that a truly flexible and integrated production system can be realized with a Petri net operation model and a hierarchical control structure. The significance of this work is related to the different operation testing and evaluation requirements encountered in manufacturing.

Improved Adhesion and Compliancy of Hierarchical Fibrillar Adhesives.

PubMed

Li, Yasong; Gates, Byron D; Menon, Carlo

2015-08-05

The gecko relies on van der Waals forces to cling onto surfaces with a variety of topography and composition. The hierarchical fibrillar structures on their climbing feet, ranging from mesoscale to nanoscale, are hypothesized to be key elements for the animal to conquer both smooth and rough surfaces. An epoxy-based artificial hierarchical fibrillar adhesive was prepared to study the influence of the hierarchical structures on the properties of a dry adhesive. The presented experiments highlight the advantages of a hierarchical structure despite a reduction of overall density and aspect ratio of nanofibrils. In contrast to an adhesive containing only nanometer-size fibrils, the hierarchical fibrillar adhesives exhibited a higher adhesion force and better compliancy when tested on an identical substrate.

Evaluating Hierarchical Structure in Music Annotations

PubMed Central

McFee, Brian; Nieto, Oriol; Farbood, Morwaread M.; Bello, Juan Pablo

2017-01-01

Music exhibits structure at multiple scales, ranging from motifs to large-scale functional components. When inferring the structure of a piece, different listeners may attend to different temporal scales, which can result in disagreements when they describe the same piece. In the field of music informatics research (MIR), it is common to use corpora annotated with structural boundaries at different levels. By quantifying disagreements between multiple annotators, previous research has yielded several insights relevant to the study of music cognition. First, annotators tend to agree when structural boundaries are ambiguous. Second, this ambiguity seems to depend on musical features, time scale, and genre. Furthermore, it is possible to tune current annotation evaluation metrics to better align with these perceptual differences. However, previous work has not directly analyzed the effects of hierarchical structure because the existing methods for comparing structural annotations are designed for “flat” descriptions, and do not readily generalize to hierarchical annotations. In this paper, we extend and generalize previous work on the evaluation of hierarchical descriptions of musical structure. We derive an evaluation metric which can compare hierarchical annotations holistically across multiple levels. sing this metric, we investigate inter-annotator agreement on the multilevel annotations of two different music corpora, investigate the influence of acoustic properties on hierarchical annotations, and evaluate existing hierarchical segmentation algorithms against the distribution of inter-annotator agreement. PMID:28824514

Falling Leaves Inspired ZnO Nanorods-Nanoslices Hierarchical Structure for Implant Surface Modification with Two Stage Releasing Features.

PubMed

Liao, Hang; Miao, Xinxin; Ye, Jing; Wu, Tianlong; Deng, Zhongbo; Li, Chen; Jia, Jingyu; Cheng, Xigao; Wang, Xiaolei

2017-04-19

Inspired from falling leaves, ZnO nanorods-nanoslices hierarchical structure (NHS) was constructed to modify the surfaces of two widely used implant materials: titanium (Ti) and tantalum (Ta), respectively. By which means, two-stage release of antibacterial active substances were realized to address the clinical importance of long-term broad-spectrum antibacterial activity. At early stages (within 48 h), the NHS exhibited a rapid releasing to kill the bacteria around the implant immediately. At a second stage (over 2 weeks), the NHS exhibited a slow releasing to realize long-term inhibition. The excellent antibacterial activity of ZnO NHS was confirmed once again by animal test in vivo. According to the subsequent experiments, the ZnO NHS coating exhibited the great advantage of high efficiency, low toxicity, and long-term durability, which could be a feasible manner to prevent the abuse of antibiotics on implant-related surgery.

Snake velvet black: Hierarchical micro- and nanostructure enhances dark colouration in Bitis rhinoceros

NASA Astrophysics Data System (ADS)

Spinner, Marlene; Kovalev, Alexander; Gorb, Stanislav N.; Westhoff, Guido

2013-05-01

The West African Gaboon viper (Bitis rhinoceros) is a master of camouflage due to its colouration pattern. Its skin is geometrically patterned and features black spots that purport an exceptional spatial depth due to their velvety surface texture. Our study shades light on micromorphology, optical characteristics and principles behind such a velvet black appearance. We revealed a unique hierarchical pattern of leaf-like microstructures striated with nanoridges on the snake scales that coincides with the distribution of black colouration. Velvet black sites demonstrate four times lower reflectance and higher absorbance than other scales in the UV - near IR spectral range. The combination of surface structures impeding reflectance and absorbing dark pigments, deposited in the skin material, provides reflecting less than 11% of the light reflected by a polytetrafluoroethylene diffuse reflectance standard in any direction. A view-angle independent black structural colour in snakes is reported here for the first time.

Characterization of a Hierarchical Network of Hyaluronic Acid/Gelatin Composite for use as a Smart Injectable Biomaterial

PubMed Central

Heris, Hossein K.; Rahmat, Meysam

2015-01-01

Hybrid HA/Ge hydrogel particles are embedded in a secondary HA network to improve their structural integrity. The internal microstructure of the particles is imaged through TEM. CSLM is used to identify the location of the Ge molecules in the microgels. Through indentation tests, the Young’s modulus of the individual particles is found to be 22 ± 2.5 kPa. The overall shear modulus of the composite is 75 ± 15 Pa at 1 Hz. The mechanical properties of the substrate are found to be viable for cell adhesion. The particles’ diameter at pH = 8 is twice that at pH = 5. The pH sensitivity is found to be appropriate for smart drug delivery. Based on their mechanical and structural properties, HA–Ge hierarchical materials may be well suited for use as injectable biomaterials for tissue reconstruction. PMID:22147507

Hierarchical, multilayered cell walls reinforced by recycled silk cocoons enhance the structural integrity of honeybee combs

PubMed Central

Zhang, Kai; Duan, Huiling; Karihaloo, Bhushan L.; Wang, Jianxiang

2010-01-01

We reveal the sophisticated and hierarchical structure of honeybee combs and measure the elastic properties of fresh and old natural honeycombs at different scales by optical microscope, environmental scanning electron microscope, nano/microindentation, and by tension and shear tests. We demonstrate that the comb walls are continuously strengthened and stiffened without becoming fragile by the addition of thin wax layers reinforced by recycled silk cocoons reminiscent of modern fiber-reinforced composite laminates. This is done to increase its margin of safety against collapse due to a temperature increase. Artificial engineering honeycombs mimic only the macroscopic geometry of natural honeycombs, but have yet to achieve the microstructural sophistication of their natural counterparts. The natural honeycombs serve as a prototype of truly biomimetic cellular materials with hitherto unattainable improvement in stiffness, strength, toughness, and thermal stability. PMID:20439765

Snake velvet black: hierarchical micro- and nanostructure enhances dark colouration in Bitis rhinoceros.

PubMed

Spinner, Marlene; Kovalev, Alexander; Gorb, Stanislav N; Westhoff, Guido

2013-01-01

The West African Gaboon viper (Bitis rhinoceros) is a master of camouflage due to its colouration pattern. Its skin is geometrically patterned and features black spots that purport an exceptional spatial depth due to their velvety surface texture. Our study shades light on micromorphology, optical characteristics and principles behind such a velvet black appearance. We revealed a unique hierarchical pattern of leaf-like microstructures striated with nanoridges on the snake scales that coincides with the distribution of black colouration. Velvet black sites demonstrate four times lower reflectance and higher absorbance than other scales in the UV-near IR spectral range. The combination of surface structures impeding reflectance and absorbing dark pigments, deposited in the skin material, provides reflecting less than 11% of the light reflected by a polytetrafluoroethylene diffuse reflectance standard in any direction. A view-angle independent black structural colour in snakes is reported here for the first time.

One-pot template-free synthesis of porous CdMoO4 microspheres and their enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Madhusudan, Puttaswamy; Zhang, Jinfeng; Yu, Jiaguo; Cheng, Bei; Xu, Difa; Zhang, Jun

2016-11-01

The optical and catalytic performances of materials strongly depend on their size, morphology, dimensionality and structure. Herein, we demonstrate a facile one-pot template free synthesis of hierarchical CdMoO4 porous microspheres via a simple low temperature oil bath method. The photoactivity of the as-prepared samples was evaluated by photocatalytic decolorization of Methyl Orange (MO) and Methylene Blue (MB) mixed dye aqueous solutions at ambient temperature under full solar spectrum. The results indicated that the concentration of ammonium molybdate and reaction time greatly influence the diameter, average crystallite size, specific surface area, pore structure and photocatalytic activity of the prepared samples. Especially, under the suitable conditions the prepared hierarchical CdMoO porous microspheres exhibited enhanced photocatalytic activity and high stability. Furthermore, it is found that the photocatalytic activity and formation rate of hydroxyl radicals greatly depend on the particle sizes and morphology of as-prepared samples. This work not only demonstrates a simple way to fabricate the hierarchical CdMoO4 porous microspheres but also shows a possibility for utilization of CdMoO4 porous microspheres for the photocatalytic treatment of waste water pollutants.

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

Immobilization of Bacillus subtilis lipase on a Cu-BTC based hierarchically porous metal-organic framework material: a biocatalyst for esterification.

PubMed

Cao, Yu; Wu, Zhuofu; Wang, Tao; Xiao, Yu; Huo, Qisheng; Liu, Yunling

2016-04-28

Bacillus subtilis lipase (BSL2) has been successfully immobilized into a Cu-BTC based hierarchically porous metal-organic framework material for the first time. The Cu-BTC hierarchically porous MOF material with large mesopore apertures is prepared conveniently by using a template-free strategy under mild conditions. The immobilized BSL2 presents high enzymatic activity and perfect reusability during the esterification reaction. After 10 cycles, the immobilized BSL2 still exhibits 90.7% of its initial enzymatic activity and 99.6% of its initial conversion.

Estimating the Term Structure With a Semiparametric Bayesian Hierarchical Model: An Application to Corporate Bonds.

PubMed

Cruz-Marcelo, Alejandro; Ensor, Katherine B; Rosner, Gary L

2011-06-01

The term structure of interest rates is used to price defaultable bonds and credit derivatives, as well as to infer the quality of bonds for risk management purposes. We introduce a model that jointly estimates term structures by means of a Bayesian hierarchical model with a prior probability model based on Dirichlet process mixtures. The modeling methodology borrows strength across term structures for purposes of estimation. The main advantage of our framework is its ability to produce reliable estimators at the company level even when there are only a few bonds per company. After describing the proposed model, we discuss an empirical application in which the term structure of 197 individual companies is estimated. The sample of 197 consists of 143 companies with only one or two bonds. In-sample and out-of-sample tests are used to quantify the improvement in accuracy that results from approximating the term structure of corporate bonds with estimators by company rather than by credit rating, the latter being a popular choice in the financial literature. A complete description of a Markov chain Monte Carlo (MCMC) scheme for the proposed model is available as Supplementary Material.

Estimating the Term Structure With a Semiparametric Bayesian Hierarchical Model: An Application to Corporate Bonds1

PubMed Central

Cruz-Marcelo, Alejandro; Ensor, Katherine B.; Rosner, Gary L.

2011-01-01

The term structure of interest rates is used to price defaultable bonds and credit derivatives, as well as to infer the quality of bonds for risk management purposes. We introduce a model that jointly estimates term structures by means of a Bayesian hierarchical model with a prior probability model based on Dirichlet process mixtures. The modeling methodology borrows strength across term structures for purposes of estimation. The main advantage of our framework is its ability to produce reliable estimators at the company level even when there are only a few bonds per company. After describing the proposed model, we discuss an empirical application in which the term structure of 197 individual companies is estimated. The sample of 197 consists of 143 companies with only one or two bonds. In-sample and out-of-sample tests are used to quantify the improvement in accuracy that results from approximating the term structure of corporate bonds with estimators by company rather than by credit rating, the latter being a popular choice in the financial literature. A complete description of a Markov chain Monte Carlo (MCMC) scheme for the proposed model is available as Supplementary Material. PMID:21765566

Nickel Ferrite Nanoparticles Anchored onto Silica Nanofibers for Designing Magnetic and Flexible Nanofibrous Membranes.

PubMed

Hong, Feifei; Yan, Chengcheng; Si, Yang; He, Jianxin; Yu, Jianyong; Ding, Bin

2015-09-16

Many applications proposed for magnetic silica nanofibers require their assembly into a cellular membrane structure. The feature to keep structure stable upon large deformation is crucial for a macroscopic porous material which functions reliably. However, it remains a key issue to realize robust flexibility in two-dimensional (2D) magnetic silica nanofibrous networks. Here, we report that the combination of electrospun silica nanofibers with zein dip-coating can lead to the formation of flexible, magnetic, and hierarchical porous silica nanofibrous membranes (SNM). The 290 nm diameter silica nanofibers act as templates for the uniform anchoring of nickel ferrite nanoparticles (size of 50 nm). Benefiting from the homogeneous and stable nanofiber-nanoparticle composite structure, the resulting magnetic SNM can maintain their structure integrity under repeated bending as high as 180° and can facilely recover. The unique hierarchical structure also provides this new class of silica membrane with integrated properties of ultralow density, high porosity, large surface area, good magnetic responsiveness, robust dye adsorption capacity, and effective emulsion separation performance. Significantly, the synthesis of such fascinating membranes may provide new insight for further application of silica in a self-supporting, structurally adaptive, and 2D membrane form.

Atomic scale chemical tomography of human bone

NASA Astrophysics Data System (ADS)

Langelier, Brian; Wang, Xiaoyue; Grandfield, Kathryn

2017-01-01

Human bone is a complex hierarchical material. Understanding bone structure and its corresponding composition at the nanometer scale is critical for elucidating mechanisms of biomineralization under healthy and pathological states. However, the three-dimensional structure and chemical nature of bone remains largely unexplored at the nanometer scale due to the challenges associated with characterizing both the structural and chemical integrity of bone simultaneously. Here, we use correlative transmission electron microscopy and atom probe tomography for the first time, to our knowledge, to reveal structures in human bone at the atomic level. This approach provides an overlaying chemical map of the organic and inorganic constituents of bone on its structure. This first use of atom probe tomography on human bone reveals local gradients, trace element detection of Mg, and the co-localization of Na with the inorganic-organic interface of bone mineral and collagen fibrils, suggesting the important role of Na-rich organics in the structural connection between mineral and collagen. Our findings provide the first insights into the hierarchical organization and chemical heterogeneity in human bone in three-dimensions at its smallest length scale - the atomic level. We demonstrate that atom probe tomography shows potential for new insights in biomineralization research on bone.

Interaction of light with hematite hierarchical structures: Experiments and simulations

NASA Astrophysics Data System (ADS)

Distaso, Monica; Zhuromskyy, Oleksander; Seemann, Benjamin; Pflug, Lukas; Mačković, Mirza; Encina, Ezequiel; Taylor, Robin Klupp; Müller, Rolf; Leugering, Günter; Spiecker, Erdmann; Peschel, Ulf; Peukert, Wolfgang

2017-03-01

Mesocrystalline particles have been recognized as a class of multifunctional materials with potential applications in different fields. However, the internal organization of nanocomposite mesocrystals and its influence on the final properties have not yet been investigated. In this paper, a novel strategy based on electrodynamic simulations is developed to shed light on how the internal structure of mesocrystals influences their optical properties. In a first instance, a unified design protocol is reported for the fabrication of hematite/PVP particles with different morphologies such as pseudo-cubes, rods-like and apple-like structures and controlled particle size distributions. The optical properties of hematite/PVP mesocrystals are effectively simulated by taking their aggregate and nanocomposite structure into consideration. The superposition T-Matrix approach accounts for the aggregate nature of mesocrystalline particles and validate the effective medium approximation used in the framework of the Mie theory and electromagnetic simulation such as Finite Element Method. The approach described in our paper provides the framework to understand and predict the optical properties of mesocrystals and more general, of hierarchical nanostructured particles.

Controllable synthesis of layered Co-Ni hydroxide hierarchical structures for high-performance hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Yuan, Peng; Zhang, Ning; Zhang, Dan; Liu, Tao; Chen, Limiao; Ma, Renzhi; Qiu, Guanzhou; Liu, Xiaohe

2016-01-01

A facile solvothermal method is developed for synthesizing layered Co-Ni hydroxide hierarchical structures by using hexamethylenetetramine (HMT) as alkaline reagent. The electrochemical measurements reveal that the specific capacitances of layered bimetallic (Co-Ni) hydroxides are generally superior to those of layered monometallic (Co, Ni) hydroxides. The as-prepared Co0.5Ni0.5 hydroxide hierarchical structures possesses the highest specific capacitance of 1767 F g-1 at a galvanic current density of 1 A g-1 and an outstanding specific capacitance retention of 87% after 1000 cycles. In comparison with the dispersed nanosheets of Co-Ni hydroxide, layered hydroxide hierarchical structures show much superior electrochemical performance. This study provides a promising method to construct hierarchical structures with controllable transition-metal compositions for enhancing the electrochemical performance in hybrid supercapacitors.

Flexible and Hierarchical Metal-Organic Framework Composites for High-Performance Catalysis.

PubMed

Huang, Ning; Drake, Hannah; Li, Jialuo; Pang, Jiangdong; Wang, Ying; Yuan, Shuai; Wang, Qi; Cai, Peiyu; Qin, Junsheng; Zhou, Hong-Cai

2018-05-18

The development of new types of porous composite materials is of great significance owing to their potentially improved performance over those of individual components and extensive applications in separation, energy storage, and heterogeneous catalysis. In this work, we integrated mesoporous metal-organic frameworks (MOFs) with macroporous melamine foam (MF) using a one-pot process, generating a series of MOF/MF composite materials with preserved crystallinity, hierarchical porosity, and increased stability over that of melamine foam. The MOF nanocrystals were threaded by the melamine foam networks, resembling a ball-and-stick model overall. As a proof-of-concept study, the resulting MOF/MF composite materials were employed as an effective heterogeneous catalyst for the epoxidation of cholesteryl esters. Combining the advantages of interpenetrative mesoporous and macroporous structures, the MOF/melamine foam composite provided higher dispersibility and more accessibility of catalytic sites, exhibiting excellent catalytic performance. This strategy constitutes an important step forward the development of other MOF composites and exploration of their high-performance catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On Hierarchical Threshold Access Structures

DTIC Science & Technology

2010-11-01

One of the recent generalizations of (t, n) secret sharing for hierarchical threshold access structures is given by Tassa, where he answers the...of theoretical background. We give a conceptually simpler alternative for the understanding of the realization of hierarchical threshold access

Application of a hierarchical structure stochastic learning automation

NASA Technical Reports Server (NTRS)

Neville, R. G.; Chrystall, M. S.; Mars, P.

1979-01-01

A hierarchical structure automaton was developed using a two state stochastic learning automato (SLA) in a time shared model. Application of the hierarchical SLA to systems with multidimensional, multimodal performance criteria is described. Results of experiments performed with the hierarchical SLA using a performance index with a superimposed noise component of ? or - delta distributed uniformly over the surface are discussed.

Use of Spherical Nanoindentation to Characterize the Anisotropic Properties of Microscale Constituents and Interfaces in Hierarchically Structured Composite Materials

DTIC Science & Technology

2015-01-24

Lilleodden, P. Anderson, J.T. Wyrobek, Acta Materialia 44 (1996) 3585-3598. [75] W.W. Gerberich, S. Venkataraman , J. Nelson, H. Huang, E. Lilleodden, W...629-644. [76] W.W. Gerberich, S.K. Venkataraman , H. Huang, S.E. Harvey, D.L. Kohlstedt, Acta Metallurgica et Materialia 43 (1995) 1569. [77] A.E

Complex Hollow Nanostructures: Synthesis and Energy-Related Applications.

PubMed

Yu, Le; Hu, Han; Wu, Hao Bin; Lou, Xiong Wen David

2017-04-01

Hollow nanostructures offer promising potential for advanced energy storage and conversion applications. In the past decade, considerable research efforts have been devoted to the design and synthesis of hollow nanostructures with high complexity by manipulating their geometric morphology, chemical composition, and building block and interior architecture to boost their electrochemical performance, fulfilling the increasing global demand for renewable and sustainable energy sources. In this Review, we present a comprehensive overview of the synthesis and energy-related applications of complex hollow nanostructures. After a brief classification, the design and synthesis of complex hollow nanostructures are described in detail, which include hierarchical hollow spheres, hierarchical tubular structures, hollow polyhedra, and multi-shelled hollow structures, as well as their hybrids with nanocarbon materials. Thereafter, we discuss their niche applications as electrode materials for lithium-ion batteries and hybrid supercapacitors, sulfur hosts for lithium-sulfur batteries, and electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. The potential superiorities of complex hollow nanostructures for these applications are particularly highlighted. Finally, we conclude this Review with urgent challenges and further research directions of complex hollow nanostructures for energy-related applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Assembling Multi-Component Nanofibers for Strong Bioinspired Underwater Adhesives

PubMed Central

Zhong, Chao; Gurry, Thomas; Cheng, Allen A; Downey, Jordan; Deng, Zhengtao; Stultz, Collin M.; Lu, Timothy K

2014-01-01

Many natural underwater adhesives harness hierarchically assembled amyloid nanostructures to achieve strong and robust interfacial adhesion under dynamic and turbulent environments. Despite recent advances, our understanding of the molecular design, self-assembly, and structure-function relationship of those natural amyloid fibers remains limited. Thus, designing biomimetic amyloid-based adhesives remains challenging. Here, we report strong and multi-functional underwater adhesives obtained from fusing mussel foot proteins (Mfps) of Mytilus galloprovincialis with CsgA proteins, the major subunit of Escherichia coli amyloid curli fibers. These hybrid molecular materials hierarchically self-assemble into higher-order structures, in which, according to molecular dynamics simulations, disordered adhesive Mfp domains are exposed on the exterior of amyloid cores formed by CsgA. Our fibers have an underwater adhesion energy approaching 20.9 mJ/m2, which is 1.5 times greater than the maximum of bio-inspired and bio-derived protein-based underwater adhesives reported thus far. Moreover, they outperform Mfps or curli fibers taken on their own at all pHs and exhibit better tolerance to auto-oxidation than Mfps at pH ≥7.0. This work establishes a platform for engineering multi-component self-assembling materials inspired by nature. PMID:25240674

Bio-Derived Hierarchical 3D Architecture from Seeds for Supercapacitor Application

NASA Astrophysics Data System (ADS)

Intawin, Pratthana; Sayed, Farheen N.; Pengpat, Kamonpan; Joyner, Jarin; Tiwary, Chandra Sekhar; Ajayan, Pulickel M.

2017-09-01

The generation and storage of green energy (energy from abundant and nonfossil) is important for a sustainable and clean future. The electrode material in a supercapacitor is a major component. The properties of these materials depend on its inherent architecture and composition. Here, we have chosen sunflower seeds and pumpkin seeds with a completely different structure to obtain a carbonaceous product. The product obtained from sunflower seed carbon is a three-dimensional hierarchical macroporous carbon (SSC) composed of many granular nanocrystals of potassium magnesium phosphate dispersed in a matrix. Contrary to this, carbon from pumpkin seeds (PSC) is revealed to be a more rigid structure, with no porous or ordered morphology. The electrochemical supercapacitive behavior was assessed by cyclic voltammetry and galvanostatic charge-discharge tests. Electrochemical measurements showed that the SSC shows a high specific capacitance of 24.9 Fg-1 as compared with that obtained (2.46 Fg-1) for PSC with a cycling efficiency of 87% and 89%, respectively. On high-temperature cycling for 500 charge-discharge cycles at 0.1 Ag-1, an improved cycling efficiency of 100% and 98% for SSC and PSC, respectively, is observed.

Wetting and Dewetting Transitions on Submerged Superhydrophobic Surfaces with Hierarchical Structures.

PubMed

Wu, Huaping; Yang, Zhe; Cao, Binbin; Zhang, Zheng; Zhu, Kai; Wu, Bingbing; Jiang, Shaofei; Chai, Guozhong

2017-01-10

The wetting transition on submersed superhydrophobic surfaces with hierarchical structures and the influence of trapped air on superhydrophobic stability are predicted based on the thermodynamics and mechanical analyses. The dewetting transition on the hierarchically structured surfaces is investigated, and two necessary thermodynamic conditions and a mechanical balance condition for dewetting transition are proposed. The corresponding thermodynamic phase diagram of reversible transition and the critical reversed pressure well explain the experimental results reported previously. Our theory provides a useful guideline for precise controlling of breaking down and recovering of superhydrophobicity by designing superhydrophobic surfaces with hierarchical structures under water.

Controlling Hydrogel Mechanics via Bio-Inspired Polymer-Nanoparticle Bond Dynamics.

PubMed

Li, Qiaochu; Barrett, Devin G; Messersmith, Phillip B; Holten-Andersen, Niels

2016-01-26

Interactions between polymer molecules and inorganic nanoparticles can play a dominant role in nanocomposite material mechanics, yet control of such interfacial interaction dynamics remains a significant challenge particularly in water. This study presents insights on how to engineer hydrogel material mechanics via nanoparticle interface-controlled cross-link dynamics. Inspired by the adhesive chemistry in mussel threads, we have incorporated iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network to obtain hydrogels cross-linked via reversible metal-coordination bonds at Fe3O4 NP surfaces. Unique material mechanics result from the supra-molecular cross-link structure dynamics in the gels; in contrast to the previously reported fluid-like dynamics of transient catechol-Fe(3+) cross-links, the catechol-Fe3O4 NP structures provide solid-like yet reversible hydrogel mechanics. The structurally controlled hierarchical mechanics presented here suggest how to develop hydrogels with remote-controlled self-healing dynamics.

Marine Structural Biomaterials in Medical Biomimicry.

PubMed

Green, David W; Lee, Jong-Min; Jung, Han-Sung

2015-10-01

Marine biomaterials display properties, behaviors, and functions that have not been artificially matched in relation to their hierarchical construction, crack-stopping properties, growth adaptation, and energy efficiency. The discovery and understanding of such features that are characteristic of natural biomaterials can be used to manufacture more energy-efficient and lightweight materials. However, a more detailed understanding of the design of natural biomaterials with good performance and the mechanism of their design is required. Far-reaching biomolecular characterization of biomaterials and biostructures from the ocean world is possible with sophisticated analytical methods, such as whole-genome RNA-seq, and de novo transcriptome sequencing and mass spectrophotometry-based sequencing. In combination with detailed material characterization, the elements in newly discovered biomaterials and their properties can be reconstituted into biomimetic or bio-inspired materials. A major aim of harnessing marine biomaterials is their translation into biomimetic counterparts. To achieve full translation, the genome, proteome, and hierarchical material characteristics, and their profiles in space and time, have to be associated to allow for smooth biomimetic translation. In this article, we highlight the novel science of marine biomimicry from a materials perspective. We focus on areas of material design and fabrication that have excelled in marine biological models, such as embedded interfaces, chiral organization, and the use of specialized composite material-on-material designs. Our emphasis is primarily on key materials with high value in healthcare in which we evaluate their future prospects. Marine biomaterials are among the most exquisite and powerful aspects in materials science today.

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

Wen, Amy M.; Podgornik, Rudolf; Strangi, Giuseppe

Sizing and shaping of mesoscale architectures with nanoscale features is a key opportunity to produce the next generation of higher-performing products and at the same time unveil completely new phenomena. This review article discusses recent advances in the design of novel photonic and plasmonic structures using a biology-inspired design. The proteinaceous capsids from viruses have long been discovered as platform technologies enabling unique applications in nanotechnology, materials, bioengineering, and medicine. In the context of materials applications, the highly organized structures formed by viral capsid proteins provide a 3D scaffold for the precise placement of plasmon and gain materials. Based onmore » their highly symmetrical structures, virus-based nanoparticles have a high propensity to self-assemble into higher-order crystalline structures, yielding hierarchical hybrid materials. Recent advances in the field have led to the development of virus-based light harvesting systems, plasmonic structures for application in high-performance metamaterials, binary nanoparticle lattices, and liquid crystalline arrays for sensing or display technologies. In conclusion, there is still much that could be explored in this area, and we foresee that this is only the beginning of great technological advances in virus-based materials for plasmonics and photonics applications.« less

Biomineralization-inspired synthesis of functional organic/inorganic hybrid materials: organic molecular control of self-organization of hybrids.

PubMed

Arakaki, Atsushi; Shimizu, Katsuhiko; Oda, Mayumi; Sakamoto, Takeshi; Nishimura, Tatsuya; Kato, Takashi

2015-01-28

Organisms produce various organic/inorganic hybrid materials, which are called biominerals. They form through the self-organization of organic molecules and inorganic elements under ambient conditions. Biominerals often have highly organized and hierarchical structures from nanometer to macroscopic length scales, resulting in their remarkable physical and chemical properties that cannot be obtained by simple accumulation of their organic and inorganic constituents. These observations motivate us to create novel functional materials exhibiting properties superior to conventional materials--both synthetic and natural. Herein, we introduce recent progress in understanding biomineralization processes at the molecular level and the development of organic/inorganic hybrid materials by these processes. We specifically outline fundamental molecular studies on silica, iron oxide, and calcium carbonate biomineralization and describe material synthesis based on these mechanisms. These approaches allow us to design a variety of advanced hybrid materials with desired morphologies, sizes, compositions, and structures through environmentally friendly synthetic routes using functions of organic molecules.

Superhydrophobicity of Hierarchical and ZNO Nanowire Coatings

DTIC Science & Technology

2014-01-01

AFRL-RX-WP-TP-2014-0141 SUPERHYDROPHOBICITY OF HIERARCHICAL ZNO NANOWIRE COATINGS (POSTPRINT) Shin Mou AFRL/RXAN JANUARY... SUPERHYDROPHOBICITY OF HIERARCHICAL ZNO NANOWIRE COATINGS (POSTPRINT) 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT...or disclose the work. The final publication is available at www.rsc.org/MaterialsA. 14. ABSTRACT Hierarchical superhydrophobic surfaces were

An Effectively Activated Hierarchical Nano-/Microspherical Li1.2Ni0.2Mn0.6O2 Cathode for Long-Life and High-Rate Lithium-Ion Batteries.

PubMed

Li, Yu; Bai, Ying; Bi, Xuanxuan; Qian, Ji; Ma, Lu; Tian, Jun; Wu, Chuan; Wu, Feng; Lu, Jun; Amine, Khalil

2016-04-07

Rechargeable lithium-ion batteries with high energy and high power density are required in the application of electric vehicles and portable electronics. Herein, we introduce a type of spherical Li-rich cathode material, Li1.2Ni0.2Mn0.6O2, assembled from uniform nanocubes by a facile polyvinylpyrrolidone (PVP)-assisted hydrothermal method. The material with a hierarchical nano-/microstructure exhibits stable high-rate performance. Furthermore, the precipitant (i.e., urea) and the structure-directing agent (i.e., PVP) effectively activated the Li2 MnO3 components in the microscale material to achieve a high specific capacity of 298.5 mAh g(-1) in the first cycle. This Li-rich cathode material still delivered 243 mAh g(-1) at 0.1 C after 200 cycles and the capacity retentions at 0.5, 1, 2, and 5 C were 94.4, 78.7, 76.3, and 67.8% after 150 cycles, respectively. The results make this Li-rich nano-/microstructure a promising cathode material for long-life and high-performance lithium-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advances and trends in structures and dynamics; Proceedings of the Symposium, Washington, DC, October 22-25, 1984

NASA Technical Reports Server (NTRS)

Noor, A. K. (Editor); Hayduk, R. J. (Editor)

1985-01-01

Among the topics discussed are developments in structural engineering hardware and software, computation for fracture mechanics, trends in numerical analysis and parallel algorithms, mechanics of materials, advances in finite element methods, composite materials and structures, determinations of random motion and dynamic response, optimization theory, automotive tire modeling methods and contact problems, the damping and control of aircraft structures, and advanced structural applications. Specific topics covered include structural design expert systems, the evaluation of finite element system architectures, systolic arrays for finite element analyses, nonlinear finite element computations, hierarchical boundary elements, adaptive substructuring techniques in elastoplastic finite element analyses, automatic tracking of crack propagation, a theory of rate-dependent plasticity, the torsional stability of nonlinear eccentric structures, a computation method for fluid-structure interaction, the seismic analysis of three-dimensional soil-structure interaction, a stress analysis for a composite sandwich panel, toughness criterion identification for unidirectional composite laminates, the modeling of submerged cable dynamics, and damping synthesis for flexible spacecraft structures.

Design Rules for Tailoring Antireflection Properties of Hierarchical Optical Structures

DOE PAGES

Leon, Juan J. Diaz; Hiszpanski, Anna M.; Bond, Tiziana C.; ...

2017-05-18

Hierarchical structures consisting of small sub-wavelength features stacked atop larger structures have been demonstrated as an effective means of reducing the reflectance of surfaces. However, optical devices require different antireflective properties depending on the application, and general unifying guidelines on hierarchical structures' design to attain a desired antireflection spectral response are still lacking. The type of reflectivity (diffuse, specular, or total/hemispherical) and its angular- and spectral-dependence are all dictated by the structural parameters. Through computational and experimental studies, guidelines have been devised to modify these various aspects of reflectivity across the solar spectrum by proper selection of the features ofmore » hierarchical structures. In this wavelength regime, micrometer-scale substructures dictate the long-wavelength spectral response and effectively reduce specular reflectance, whereas nanometer-scale substructures dictate primarily the visible wavelength spectral response and reduce diffuse reflectance. Coupling structures having these two length scales into hierarchical arrays impressively reduces surfaces' hemispherical reflectance across a broad spectrum of wavelengths and angles. Furthermore, such hierarchical structures in silicon are demonstrated having an average total reflectance across the solar spectrum of 1.1% (average weighted reflectance of 1% in the 280–2500 nm range of the AM 1.5 G spectrum) and specular reflectance <1% even at angles of incidence as high as 67°.« less

Two-Dimensional Fullerene Assembly from an Exfoliated van der Waals Template.

PubMed

Lee, Kihong; Choi, Bonnie; Plante, Ilan Jen-La; Paley, Maria V; Zhong, Xinjue; Crowther, Andrew C; Owen, Jonathan S; Zhu, Xiaoyang; Roy, Xavier

2018-05-22

Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C 60 as a polymerizable monomer. The C 60 building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C 60 monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C 60 . The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Defect Engineering toward Atomic Co-Nx -C in Hierarchical Graphene for Rechargeable Flexible Solid Zn-Air Batteries.

PubMed

Tang, Cheng; Wang, Bin; Wang, Hao-Fan; Zhang, Qiang

2017-10-01

Rechargeable flexible solid Zn-air battery, with a high theoretical energy density of 1086 Wh kg -1 , is among the most attractive energy technologies for future flexible and wearable electronics; nevertheless, the practical application is greatly hindered by the sluggish oxygen reduction reaction/oxygen evolution reaction (ORR/OER) kinetics on the air electrode. Precious metal-free functionalized carbon materials are widely demonstrated as the most promising candidates, while it still lacks effective synthetic methodology to controllably synthesize carbocatalysts with targeted active sites. This work demonstrates the direct utilization of the intrinsic structural defects in nanocarbon to generate atomically dispersed Co-N x -C active sites via defect engineering. As-fabricated Co/N/O tri-doped graphene catalysts with highly active sites and hierarchical porous scaffolds exhibit superior ORR/OER bifunctional activities and impressive applications in rechargeable Zn-air batteries. Specifically, when integrated into a rechargeable and flexible solid Zn-air battery, a high open-circuit voltage of 1.44 V, a stable discharge voltage of 1.19 V, and a high energy efficiency of 63% at 1.0 mA cm -2 are achieved even under bending. The defect engineering strategy provides a new concept and effective methodology for the full utilization of nanocarbon materials with various structural features and further development of advanced energy materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alumina-coated and manganese monoxide embedded 3D carbon derived from avocado as high-performance anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

rehman, Wasif ur; Xu, Youlong; Du, Xianfeng; Sun, Xiaofei; Ullah, Inam; Zhang, Yuan; Jin, Yanling; Zhang, Baofeng; Li, Xifei

2018-07-01

Derived from avocado fruit, a three dimension (3D) carbon is prepared via a hydrothermal/pyrolysis process followed by embedding with MnO nanoparticles by a wet chemical method and coating with Al2O3 through an atomic layer deposition technique. The obtained material presents a hierarchical structure that MnO nanocrystals wrapped in 3D carbon and then encapsulated in a uniform Al2O3 layer with a thickness of about 5 nm. Benefiting from this hierarchical structure in which 3D carbon offers numerous electronic pathways to enhance the conductivity and Al2O3 nanolayer provide a shelter to keep away from dissolution of Mn4+ and volume changes during charge/discharge process. This material (marked as C/MnO@Al2O3) has exhibited high rate performance and excellent cyclability as an anode for lithium ion batteries. A high specific capacity of about 600 mA h g-1 is achieved at a current density of 1000 mA g-1 and the electrode can still deliver a high specific capacity of about 1165 mA h g-1 at 150 mA g-1 after 100 cycles. These results facilitate a green and high potential of anode materials towards promising devices for advance performance of lithium-ion batteries.

Three-Dimensional Graphene-Carbon Nanotube-Ni Hierarchical Architecture as a Polysulfide Trap for Lithium-Sulfur Batteries.

PubMed

Gnana Kumar, G; Chung, Sheng-Heng; Raj Kumar, T; Manthiram, Arumugam

2018-06-20

Despite their high energy density and affordable cost compared to lithium-ion (Li-ion) batteries, lithium-sulfur (Li-S) batteries still endure from slow reaction kinetics and capacity loss induced by the insulating sulfur and severe polysulfide diffusion. To address these issues, we report here nickel nanoparticles filled in vertically grown carbon nanotubes (CNTs) on graphene sheets (graphene-CNT-nickel composite (Gr-CNT-Ni)) that are coated onto a polypropylene separator as a polysulfide trap for the construction of high-loading sulfur cathodes. The hierarchical porous framework of Gr-CNT physically entraps and immobilizes the active material sulfur, while the strong chemical interaction with Ni nanoparticles in Gr-CNT-Ni inhibits polysulfide diffusion. The covalently interconnected electron conduction channels and carbon shell-confined metal active sites provide feasible paths for the continual regeneration of active material during the charge-discharge process. Benefitting from these novel morphological and structural features, the Li-S cell with the Gr-CNT-Ni as a polysulfide trap demonstrates high specific capacity and good cycle life. This work provides new avenues for synergistically combining the advantages of hierarchical porous carbon architectures and metal active sites for the development of high-performance cathodes for Li-S batteries.

Hierarchical Nanostructures of Nitrogen-Doped Porous Carbon Polyhedrons Confined in Carbon Nanosheets for High-Performance Supercapacitors.

PubMed

Zhao, Zhe; Liu, Siliang; Zhu, Jixin; Xu, Jingsan; Li, Le; Huang, Zhaoqi; Zhang, Chao; Liu, Tianxi

2018-05-31

Interconnected close-packed nitrogen-doped porous carbon polyhedrons (NCPs) confined in two-dimensional carbon nanosheets (CNSs) have been prepared through a sustainable one-pot pyrolysis of a simple solid mixture of zeolitic imidazolate framework-8 (ZIF-8) crystals and with organic potassium as the precursors. The hierarchically organized framework of the NCP-CNS composites enables NCPs and CNSs to act as well-defined electrolyte reservoirs and mechanical buffers accommodating large volume expansions of NCPs, respectively. Among the unique composite nanostructures, the NCPs with vast micropores provide electric double-layer capacitances, while the CNSs bridge the individual NCPs to form a conductive pathway with a hierarchical porosity. As a result, the NCP-CNS composites with high electrical integrity and structural stability are used as electrode materials for high-performance supercapacitors, which exhibit excellent electrochemical capacitive characteristics in terms of an outstanding capacitance of 300 F g -1 at 1 A g -1 , large energy density of 20.9 W h kg -1 , and great cycling performance of 100% retention after 6000 cycles. This work therefore presents a one-pot and efficient strategy to prepare an ordered arrangement of ZIF-8-derived porous carbons toward new electrode materials in promising energy storage systems.

Size-dependent elastic/inelastic behavior of enamel over millimeter and nanometer length scales.

PubMed

Ang, Siang Fung; Bortel, Emely L; Swain, Michael V; Klocke, Arndt; Schneider, Gerold A

2010-03-01

The microstructure of enamel like most biological tissues has a hierarchical structure which determines their mechanical behavior. However, current studies of the mechanical behavior of enamel lack a systematic investigation of these hierarchical length scales. In this study, we performed macroscopic uni-axial compression tests and the spherical indentation with different indenter radii to probe enamel's elastic/inelastic transition over four hierarchical length scales, namely: 'bulk enamel' (mm), 'multiple-rod' (10's microm), 'intra-rod' (100's nm with multiple crystallites) and finally 'single-crystallite' (10's nm with an area of approximately one hydroxyapatite crystallite). The enamel's elastic/inelastic transitions were observed at 0.4-17 GPa depending on the length scale and were compared with the values of synthetic hydroxyapatite crystallites. The elastic limit of a material is important as it provides insights into the deformability of the material before fracture. At the smallest investigated length scale (contact radius approximately 20 nm), elastic limit is followed by plastic deformation. At the largest investigated length scale (contact size approximately 2 mm), only elastic then micro-crack induced response was observed. A map of elastic/inelastic regions of enamel from millimeter to nanometer length scale is presented. Possible underlying mechanisms are also discussed. (c) 2009 Elsevier Ltd. All rights reserved.

Coralline-Like N-Doped Hierarchically Porous Carbon Derived from Enteromorpha as a Host Matrix for Lithium-Sulfur Battery.

PubMed

Ji, Shengnan; Imtiaz, Sumair; Sun, Dan; Xin, Ying; Li, Qian; Huang, Taizhong; Zhang, Zhaoliang; Huang, Yunhui

2017-12-22

Coralline-like N-doped hierarchically porous carbon (CNHPC) was prepared through a hydrothermal carbonization process using a sea pollutant enteromorpha as the starting material. The addition of a small amount of glucose during carbonization improved the yield of carbon, and the inherent N contents, especially for pyrrolic N and pyridinic N atoms. After loading 40 wt. % sulfur, the CNHPC/S composite, as a cathode in a Li-S battery, exhibited an initial discharge capacity of 1617 mAh g -1 (96.5 % of theoretical capacity) at 0.1 C and a capacity loss of 0.05 % per charge-discharge cycle after 500 cycles at 0.5 C with a stable Coulombic efficiency of 100 % in carbonate based electrolyte. Such a great performance can be attributed to the coralline-like hierarchically porous infrastructure and inherently abundant N doping. Given the conversion of waste pollutants into valuable energy-storage materials and the easy process, this work features a promising approach to prepare C/S cathodes for Li-S batteries. The special structural and textural characteristics of CNHPC might be attractive to other practical applications such as supercapacitors and catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraordinary Thermoelectric Performance Realized in Hierarchically Structured AgSbSe2 with Ultralow Thermal Conductivity.

PubMed

Gao, Weihong; Wang, Zhenyou; Huang, Jin; Liu, Zihang

2018-05-24

Thermoelectric conversion from low-grade heat to electricity is regarded as the highly reliable and environmentally friendly technology in energy-harvesting area. However, how to develop efficient thermoelectric materials using a simple fabrication method is still a critical challenge in thermoelectric community. Here, we first fabricate the high thermoelectric performance of Ca-doped AgSbSe 2 with a hierarchical microstructure using a facile approach, namely, mechanical alloying (for only 30 min) and a quick hot-pressing method. The hierarchical microstructure, including point defects (atomic scale), dislocations, and nanoprecipitates (nanoscale) as well as grain boundaries (microscale), strongly scatters phonons with comparable sizes without deterioration of carrier mobility. Because of the higher carrier concentration of nanostructured AgSbSe 2 than that of coarse-grain AgSbSe 2 , power factor can also be improved slightly after nanostructuring. Ca doping further optimizes the carrier concentration and creates the point-defect scattering of phonons, leading to the ultralow lattice thermal conductivity ∼0.27 W m -1 K -1 at 673 K and thus largely improving the peak ZT up to 1.2. The high thermoelectric performance in combination with a facile fabrication method highlights AgSbSe 2 -based materials as robust thermoelectric candidates for energy harvesting.

Chosen aspects of multi-criteria analysis applied to support the choice of materials for building structures

NASA Astrophysics Data System (ADS)

Szafranko, E.

2017-08-01

When planning a building structure, dilemmas arise as to what construction and material solutions are feasible. The decisions are not always obvious. A procedure for selecting the variant that will best satisfy the expectations of the investor and future users of a structure must be founded on mathematical methods. The following deserve special attention: the MCE methods, Hierarchical Analysis Methods and Weighting Methods. Another interesting solution, particularly useful when dealing with evaluations which take into account negative values, is the Indicator Method. MCE methods are relatively popular owing to the simplicity of the calculations and ease of the interpretation of the results. Having prepared the input data properly, they enable the user to compare them on the same level. In a situation where an analysis involves a large number of data, it is more convenient to divide them into groups according to main criteria and subcriteria. This option is provided by hierarchical analysis methods. They are based on ordered sets of criteria, which are evaluated in groups. In some cases, this approach yields the results that are superior and easier to read. If an analysis encompasses direct and indirect effects, an Indicator Method seems to be a justified choice for selecting the right solution. The Indicator Method is different in character and relies on weights and assessments of effects. It allows the user to evaluate effectively the analyzed variants. This article explains the methodology of conducting a multi-criteria analysis, showing its advantages and disadvantages. An example of calculations contained in the article shows what problems can be encountered when making an assessment of various solutions regarding building materials and structures. For comparison, an analysis based on graphical methods developed by the author was presented.

Culture Modulates the Brain Response to Harmonic Violations: An EEG Study on Hierarchical Syntactic Structure in Music.

PubMed

Akrami, Haleh; Moghimi, Sahar

2017-01-01

We investigated the role of culture in processing hierarchical syntactic structures in music. We examined whether violation of non-local dependencies manifest in event related potentials (ERP) for Western and Iranian excerpts by recording EEG while participants passively listened to sequences of modified/original excerpts. We also investigated oscillatory and synchronization properties of brain responses during processing of hierarchical structures. For the Western excerpt, subjective ratings of conclusiveness were marginally significant and the difference in the ERP components fell short of significance. However, ERP and behavioral results showed that while listening to culturally familiar music, subjects comprehended whether or not the hierarchical syntactic structure was fulfilled. Irregularities in the hierarchical structures of the Iranian excerpt elicited an early negativity in the central regions bilaterally, followed by two later negativities from 450-700 to 750-950 ms. The latter manifested throughout the scalp. Moreover, violations of hierarchical structure in the Iranian excerpt were associated with (i) an early decrease in the long range alpha phase synchronization, (ii) an early increase in the oscillatory activity in the beta band over the central areas, and (iii) a late decrease in the theta band phase synchrony between left anterior and right posterior regions. Results suggest that rhythmic structures and melodic fragments, representative of Iranian music, created a familiar context in which recognition of complex non-local syntactic structures was feasible for Iranian listeners. Processing of neural responses to the Iranian excerpt indicated neural mechanisms for processing of hierarchical syntactic structures in music at different levels of cortical integration.

Masking effects of speech and music: does the masker's hierarchical structure matter?

PubMed

Shi, Lu-Feng; Law, Yvonne

2010-04-01

Speech and music are time-varying signals organized by parallel hierarchical rules. Through a series of four experiments, this study compared the masking effects of single-talker speech and instrumental music on speech perception while manipulating the complexity of hierarchical and temporal structures of the maskers. Listeners' word recognition was found to be similar between hierarchically intact and disrupted speech or classical music maskers (Experiment 1). When sentences served as the signal, significantly greater masking effects were observed with disrupted than intact speech or classical music maskers (Experiment 2), although not with jazz or serial music maskers, which differed from the classical music masker in their hierarchical structures (Experiment 3). Removing the classical music masker's temporal dynamics or partially restoring it affected listeners' sentence recognition; yet, differences in performance between intact and disrupted maskers remained robust (Experiment 4). Hence, the effect of structural expectancy was largely present across maskers when comparing them before and after their hierarchical structure was purposefully disrupted. This effect seemed to lend support to the auditory stream segregation theory.

Three-Dimensional Hierarchical NixCo1-xO/NiyCo2-yP@C Hybrids on Nickel Foam for Excellent Supercapacitors.

PubMed

Shao, Yubo; Zhao, Yongqing; Li, Hua; Xu, Cailing

2016-12-28

Active materials and special structures of the electrode have decisive influence on the electrochemical properties of supercapacitors. Herein, three-dimensional (3D) hierarchical Ni x Co 1-x O/Ni y Co 2-y P@C (denoted as NiCoOP@C) hybrids have been successfully prepared by a phosphorization treatment of hierarchical Ni x Co 1-x O@C grown on nickel foam. The resulting NiCoOP@C hybrids exhibit an outstanding specific capacitance and cycle performance because they couple the merits of the superior cycling stability of Ni x Co 1-x O, the high specific capacitance of Ni y Co 2-y P, the mechanical stability of carbon layer, and the 3D hierarchical structure. The specific capacitance of 2638 F g -1 can be obtained at the current density of 1 A g -1 , and even at the current density of 20 A g -1 , the NiCoOP@C electrode still possesses a specific capacitance of 1144 F g -1 . After 3000 cycles at 10 A g -1 , 84% of the initial specific capacitance is still remained. In addition, an asymmetric ultracapacitor (ASC) is assembled through using NiCoOP@C hybrids as anode and activated carbon as cathode. The as-prepared ASC obtains a maximum energy density of 39.4 Wh kg -1 at a power density of 394 W kg -1 and still holds 21 Wh kg -1 at 7500 W kg -1 .

Construction of Hierarchical CuO/Cu2O@NiCo2S4 Nanowire Arrays on Copper Foam for High Performance Supercapacitor Electrodes

PubMed Central

Zhou, Luoxiao; He, Ying; Jia, Congpu; Pavlinek, Vladimir; Saha, Petr; Cheng, Qilin

2017-01-01

Hierarchical copper oxide @ ternary nickel cobalt sulfide (CuO/Cu2O@NiCo2S4) core-shell nanowire arrays on Cu foam have been successfully constructed by a facile two-step strategy. Vertically aligned CuO/Cu2O nanowire arrays are firstly grown on Cu foam by one-step thermal oxidation of Cu foam, followed by electrodeposition of NiCo2S4 nanosheets on the surface of CuO/Cu2O nanowires to form the CuO/Cu2O@NiCo2S4 core-shell nanostructures. Structural and morphological characterizations indicate that the average thickness of the NiCo2S4 nanosheets is ~20 nm and the diameter of CuO/Cu2O core is ~50 nm. Electrochemical properties of the hierarchical composites as integrated binder-free electrodes for supercapacitor were evaluated by various electrochemical methods. The hierarchical composite electrodes could achieve ultrahigh specific capacitance of 3.186 F cm−2 at 10 mA cm−2, good rate capability (82.06% capacitance retention at the current density from 2 to 50 mA cm−2) and excellent cycling stability, with capacitance retention of 96.73% after 2000 cycles at 10 mA cm−2. These results demonstrate the significance of optimized design and fabrication of electrode materials with more sufficient electrolyte-electrode interface, robust structural integrity and fast ion/electron transfer. PMID:28914819

* Hierarchically Structured Electrospun Scaffolds with Chemically Conjugated Growth Factor for Ligament Tissue Engineering.

PubMed

Pauly, Hannah M; Sathy, Binulal N; Olvera, Dinorath; McCarthy, Helen O; Kelly, Daniel J; Popat, Ketul C; Dunne, Nicholas J; Haut Donahue, Tammy Lynn

2017-08-01

The anterior cruciate ligament (ACL) of the knee is vital for proper joint function and is commonly ruptured during sports injuries or car accidents. Due to a lack of intrinsic healing capacity and drawbacks with allografts and autografts, there is a need for a tissue-engineered ACL replacement. Our group has previously used aligned sheets of electrospun polycaprolactone nanofibers to develop solid cylindrical bundles of longitudinally aligned nanofibers. We have shown that these nanofiber bundles support cell proliferation and elongation and the hierarchical structure and material properties are similar to the native human ACL. It is possible to combine multiple nanofiber bundles to create a scaffold that attempts to mimic the macroscale structure of the ACL. The goal of this work was to develop a hierarchical bioactive scaffold for ligament tissue engineering using connective tissue growth factor (CTGF)-conjugated nanofiber bundles and evaluate the behavior of mesenchymal stem cells (MSCs) on these scaffolds in vitro and in vivo. CTGF was immobilized onto the surface of individual nanofiber bundles or scaffolds consisting of multiple nanofiber bundles. The conjugation efficiency and the release of conjugated CTGF were assessed using X-ray photoelectron spectroscopy, assays, and immunofluorescence staining. Scaffolds were seeded with MSCs and maintained in vitro for 7 days (individual nanofiber bundles), in vitro for 21 days (scaled-up scaffolds of 20 nanofiber bundles), or in vivo for 6 weeks (small scaffolds of 4 nanofiber bundles), and ligament-specific tissue formation was assessed in comparison to non-CTGF-conjugated control scaffolds. Results showed that CTGF conjugation encouraged cell proliferation and ligament-specific tissue formation in vitro and in vivo. The results suggest that hierarchical electrospun nanofiber bundles conjugated with CTGF are a scalable and bioactive scaffold for ACL tissue engineering.

An Analysis of Turkey's PISA 2015 Results Using Two-Level Hierarchical Linear Modelling

ERIC Educational Resources Information Center

Atas, Dogu; Karadag, Özge

2017-01-01

In the field of education, most of the data collected are multi-level structured. Cities, city based schools, school based classes and finally students in the classrooms constitute a hierarchical structure. Hierarchical linear models give more accurate results compared to standard models when the data set has a structure going far as individuals,…

Ray tracing a three-dimensional scene using a hierarchical data structure

DOEpatents

Wald, Ingo; Boulos, Solomon; Shirley, Peter

2012-09-04

Ray tracing a three-dimensional scene made up of geometric primitives that are spatially partitioned into a hierarchical data structure. One example embodiment is a method for ray tracing a three-dimensional scene made up of geometric primitives that are spatially partitioned into a hierarchical data structure. In this example embodiment, the hierarchical data structure includes at least a parent node and a corresponding plurality of child nodes. The method includes a first act of determining that a first active ray in the packet hits the parent node and a second act of descending to each of the plurality of child nodes.

Hierarchical macroscopic fibrillar adhesives: in situ study of buckling and adhesion mechanisms on wavy substrates.

PubMed

Bauer, Christina T; Kroner, Elmar; Fleck, Norman A; Arzt, Eduard

2015-10-23

Nature uses hierarchical fibrillar structures to mediate temporary adhesion to arbitrary substrates. Such structures provide high compliance such that the flat fibril tips can be better positioned with respect to asperities of a wavy rough substrate. We investigated the buckling and adhesion of hierarchically structured adhesives in contact with flat smooth, flat rough and wavy rough substrates. A macroscopic model for the structural adhesive was fabricated by molding polydimethylsiloxane into pillars of diameter in the range of 0.3-4.8 mm, with up to three different hierarchy levels. Both flat-ended and mushroom-shaped hierarchical samples buckled at preloads one quarter that of the single level structures. We explain this behavior by a change in the buckling mode; buckling leads to a loss of contact and diminishes adhesion. Our results indicate that hierarchical structures can have a strong influence on the degree of adhesion on both flat and wavy substrates. Strategies are discussed that achieve highly compliant substrates which adhere to rough substrates.

Effects of hierarchical structures and insulating liquid media on adhesion

NASA Astrophysics Data System (ADS)

Yang, Weixu; Wang, Xiaoli; Li, Hanqing; Song, Xintao

2017-11-01

Effects of hierarchical structures and insulating liquid media on adhesion are investigated through a numerical adhesive contact model established in this paper, in which hierarchical structures are considered by introducing the height distribution into the surface gap equation, and media are taken into account through the Hamaker constant in Lifshitz-Hamaker approach. Computational methods such as inexact Newton method, bi-conjugate stabilized (Bi-CGSTAB) method and fast Fourier transform (FFT) technique are employed to obtain the adhesive force. It is shown that hierarchical structured surface exhibits excellent anti-adhesive properties compared with flat, micro or nano structured surfaces. Adhesion force is more dependent on the sizes of nanostructures than those of microstructures, and the optimal ranges of nanostructure pitch and maximum height for small adhesion force are presented. Insulating liquid media effectively decrease the adhesive interaction and 1-bromonaphthalene exhibits the smallest adhesion force among the five selected media. In addition, effects of hierarchical structures with optimal sizes on reducing adhesion are more obvious than those of the selected insulating liquid media.

Applying macromolecular crowding to 3D bioprinting: fabrication of 3D hierarchical porous collagen-based hydrogel constructs.

PubMed

Ng, Wei Long; Goh, Min Hao; Yeong, Wai Yee; Naing, May Win

2018-02-27

Native tissues and/or organs possess complex hierarchical porous structures that confer highly-specific cellular functions. Despite advances in fabrication processes, it is still very challenging to emulate the hierarchical porous collagen architecture found in most native tissues. Hence, the ability to recreate such hierarchical porous structures would result in biomimetic tissue-engineered constructs. Here, a single-step drop-on-demand (DOD) bioprinting strategy is proposed to fabricate hierarchical porous collagen-based hydrogels. Printable macromolecule-based bio-inks (polyvinylpyrrolidone, PVP) have been developed and printed in a DOD manner to manipulate the porosity within the multi-layered collagen-based hydrogels by altering the collagen fibrillogenesis process. The experimental results have indicated that hierarchical porous collagen structures could be achieved by controlling the number of macromolecule-based bio-ink droplets printed on each printed collagen layer. This facile single-step bioprinting process could be useful for the structural design of collagen-based hydrogels for various tissue engineering applications.