Periodically ordered nanohetero inorganic structures of nanoparticles, nanorods and layers in a matrix from self-assembled block copolymers

2014 ◽  
Vol 1706 ◽  
Author(s):  
Hiroaki Wakayama ◽  
Hirotaka Yonekura ◽  
Yasuaki Kawai

ABSTRACTPeriodically ordered nanohetero inorganic structures offer great promise due to their unique electric, ionic, magnetic, and photonic properties. Many studies have focused on the formation of periodically ordered nano-hetero inorganic structures through layer-by-layer adsorption, sputtering, and self-assembly methods. However, the construction of three-dimensional periodically ordered nanohetero inorganic structures with desired sizes and morphologies remains a great challenge. We present a simple method for producing three-dimensional periodically ordered inorganic nanoheterostructures with controlled shape and size by replicating self-assembled block copolymers (BCPs) containing precursors of metals and metal oxides. Precursors were dissolved with BCPs in a solvent. Upon evaporation of the solvent, each precursor was selectively introduced into a separate polymer block. Application of an external magnetic field (10 T) to the BCP-precursor composites resulted in a phase transition of from spheres to hexagonal cylinders. Subsequent pyrolytic removal of the BCPs produced periodically ordered nanoheterostructures that were structural replicates of the precursor–BCP composites. Self-assembled nano-hetero inorganic structures of nanoparticles, nanorods and layers in a matrix were produced. The morphology and domain size can be tailored by controlling the molecular weight and relative block length of block copolymers. The controlled size and morphology of the inorganic nanoheterostructures demonstrate the method’s utility for producing highly functional materials.

2020 ◽  
Vol 6 (24) ◽  
pp. eaaz7202 ◽  
Author(s):  
Bijal B. Patel ◽  
Dylan J. Walsh ◽  
Do Hoon Kim ◽  
Justin Kwok ◽  
Byeongdu Lee ◽  
...  

Additive manufacturing of functional materials is limited by control of microstructure and assembly at the nanoscale. In this work, we integrate nonequilibrium self-assembly with direct-write three-dimensional (3D) printing to prepare bottlebrush block copolymer (BBCP) photonic crystals (PCs) with tunable structure color. After varying deposition conditions during printing of a single ink solution, peak reflected wavelength for BBCP PCs span a range of 403 to 626 nm (blue to red), corresponding to an estimated change in d-spacing of >70 nm (Bragg- Snell equation). Physical characterization confirms that these vivid optical effects are underpinned by tuning of lamellar domain spacing, which we attribute to modulation of polymer conformation. Using in situ optical microscopy and solvent-vapor annealing, we identify kinetic trapping of metastable microstructures during printing as the mechanism for domain size control. More generally, we present a robust processing scheme with potential for on-the-fly property tuning of a variety of functional materials.


Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2572
Author(s):  
Jaleesa Bresseleers ◽  
Mahsa Bagheri ◽  
Coralie Lebleu ◽  
Sébastien Lecommandoux ◽  
Olivier Sandre ◽  
...  

The careful design of nanoparticles, in terms of size and morphology, is of great importance to developing effective drug delivery systems. The ability to precisely tailor nanoparticles in size and morphology during polymer self-assembly was therefore investigated. Four poly(ethylene glycol)-b-poly(N-2-benzoyloxypropyl methacrylamide) mPEG-b-p(HPMA-Bz) block copolymers with a fixed hydrophilic block of mPEG 5 kDa and a varying molecular weight of the hydrophobic p(HPMA-Bz) block (A: 17.1, B: 10.0, C: 5.2 and D: 2.7 kDa) were self-assembled into nanoparticles by nanoprecipitation under well-defined flow conditions, using microfluidics, at different concentrations. The nanoparticles from polymer A, increased in size from 55 to 90 nm using lower polymer concentrations and slower flow rates and even polymer vesicles were formed along with micelles. Similarly, nanoparticles from polymer D increased in size from 35 to 70 nm at slower flow rates and also formed vesicles along with micelles, regardless of the used concentration. Differently, polymers B and C mainly self-assembled into micelles at the different applied flow rates with negligible size difference. In conclusion, this study demonstrates that the self-assembly of mPEG-b-p(HPMA-Bz) block copolymers can be easily tailored in size and morphology using microfluidics and is therefore an attractive option for further scaled-up production activities.


MRS Advances ◽  
2020 ◽  
Vol 5 (64) ◽  
pp. 3507-3520
Author(s):  
Chunhui Dai ◽  
Kriti Agarwal ◽  
Jeong-Hyun Cho

AbstractNanoscale self-assembly, as a technique to transform two-dimensional (2D) planar patterns into three-dimensional (3D) nanoscale architectures, has achieved tremendous success in the past decade. However, an assembly process at nanoscale is easily affected by small unavoidable variations in sample conditions and reaction environment, resulting in a low yield. Recently, in-situ monitored self-assembly based on ion and electron irradiation has stood out as a promising candidate to overcome this limitation. The usage of ion and electron beam allows stress generation and real-time observation simultaneously, which significantly enhances the controllability of self-assembly. This enables the realization of various complex 3D nanostructures with a high yield. The additional dimension of the self-assembled 3D nanostructures opens the possibility to explore novel properties that cannot be demonstrated in 2D planar patterns. Here, we present a rapid review on the recent achievements and challenges in nanoscale self-assembly using electron and ion beam techniques, followed by a discussion of the novel optical properties achieved in the self-assembled 3D nanostructures.


Micromachines ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 13 ◽  
Author(s):  
Bin Zhang ◽  
Jaehyun Lee ◽  
Mincheol Kim ◽  
Naeeung Lee ◽  
Hyungdong Lee ◽  
...  

The macroscopic assembly of two-dimensional materials into a laminar structure has received considerable attention because it improves both the mechanical and chemical properties of the original materials. However, conventional manufacturing methods have certain limitations in that they require a high temperature process, use toxic solvents, and are considerably time consuming. Here, we present a new system for the self-assembly of layer-by-layer (LBL) graphene oxide (GO) via an electrohydrodynamic (EHD) jet printing technique. During printing, the orientation of GO flakes can be controlled by the velocity distribution of liquid jet and electric field-induced alignment spontaneously. Closely-packed GO patterns with an ordered laminar structure can be rapidly realized using an interfacial assembly process on the substrates. The surface roughness and electrical conductivity of the LBL structure were significantly improved compared with conventional dispensing methods. We further applied this technique to fabricate a reduced graphene oxide (r-GO)-based supercapacitor and a three-dimensional (3D) metallic grid hybrid ammonia sensor. We present the EHD-assisted assembly of laminar r-GO structures as a new platform for preparing high-performance energy storage devices and sensors.


2015 ◽  
Vol 3 (4) ◽  
pp. 1540-1548 ◽  
Author(s):  
Sheng Zhu ◽  
Hui Zhang ◽  
Ping Chen ◽  
Lin-Hui Nie ◽  
Chuan-Hao Li ◽  
...  

A facile protocol for the self-assembly of the rGO/β-MnO2 hybrid hydrogel with ultrafine structure and precise control of mass-loading for high performance supercapacitors is reported.


2009 ◽  
Vol 65 (3) ◽  
pp. m139-m142 ◽  
Author(s):  
Rajesh Koner ◽  
Israel Goldberg

The title compound, (5,10,15,20-tetra-4-pyridylporphyrinato)zinc(II) 1,2-dichlorobenzene disolvate, [Zn(C40H24N8)]·2C6H4Cl2, contains a clathrate-type structure. It is composed of two-dimensional square-grid coordination networks of the self-assembled porphyrin moiety, which are stacked one on top of the other in a parallel manner. The interporphyrin cavities of the overlapping networks combine into channel voids accommodated by the dichlorobenzene solvent. Molecules of the porphyrin complex are located on crystallographic inversion centres. The observed two-dimensional assembly mode of the porphyrin units represents a supramolecular isomer of the unique three-dimensional coordination frameworks of the same porphyrin building block observed earlier. The significance of this study lies in the discovery of an additional supramolecular isomer of the rarely observed structures of metalloporphyrins self-assembled directly into extended coordination polymers without the use of external ligand or metal ion auxiliaries.


RSC Advances ◽  
2018 ◽  
Vol 8 (18) ◽  
pp. 9963-9969 ◽  
Author(s):  
Zhe Wang ◽  
Min Xue ◽  
Herong Zhang ◽  
Zihui Meng ◽  
Kenneth J. Shea ◽  
...  

A simple and low-cost humidity sensor based on self-assembled three dimensional nanohydrogel colloidal array was prepared for humidity sensing.


2021 ◽  
Vol 43 ◽  
pp. 103195
Author(s):  
Jie Xu ◽  
Jing Liang ◽  
Yongjin Zou ◽  
Fen Xu ◽  
Qiaohong Chen ◽  
...  

2020 ◽  
Vol 117 (26) ◽  
pp. 14667-14675 ◽  
Author(s):  
Mingchao Zhang ◽  
Rui Guo ◽  
Ke Chen ◽  
Yiliang Wang ◽  
Jiali Niu ◽  
...  

Many natural materials possess built-in structural variation, endowing them with superior performance. However, it is challenging to realize programmable structural variation in self-assembled synthetic materials since self-assembly processes usually generate uniform and ordered structures. Here, we report the formation of asymmetric microribbons composed of directionally self-assembled two-dimensional nanoflakes in a polymeric matrix during three-dimensional direct-ink printing. The printed ribbons with embedded structural variations show site-specific variance in their mechanical properties. Remarkably, the ribbons can spontaneously transform into ultrastretchable springs with controllable helical architecture upon stimulation. Such springs also exhibit superior nanoscale transport behavior as nanofluidic ionic conductors under even ultralarge tensile strains (>1,000%). Furthermore, to show possible real-world uses of such materials, we demonstrate in vivo neural recording and stimulation using such springs in a bullfrog animal model. Thus, such springs can be used as neural electrodes compatible with soft and dynamic biological tissues.


2020 ◽  
Vol 7 (8) ◽  
pp. 200642
Author(s):  
Syed Kumail Abbas ◽  
Ghulam M. Mustafa ◽  
Murtaza Saleem ◽  
Muhammad Sufyan ◽  
Saira Riaz ◽  
...  

Controlled growth of nanostructures plays a vital role in tuning the physical and chemical properties of functional materials for advanced energy and memory storage devices. Herein, we synthesized hierarchical micro-sized flowers, built by the self-assembly of highly crystalline, two-dimensional nanoplates of Co- and Ni-doped BiFeO 3 , using a simple ethylene glycol-mediated solvothermal method. Pure BiFeO 3 attained scattered one-dimensional nanorods-type morphology having diameter nearly 60 nm. Co-doping of Co and Ni at Fe-site in BiFeO 3 does not destabilize the morphology; rather it generates three-dimensional floral patterns of self-assembled nanoplates. Unsaturated polarization loops obtained for BiFeO 3 confirmed the leakage behaviour of these rhombohedrally distorted cubic perovskites. These loops were then used to determine the energy density of the BiFeO 3 perovskites. Enhanced ferromagnetic behaviour with high coercivity and remanence was observed for these nanoplates. A detailed discussion about the origin of ferromagnetic behaviour based on Goodenough–Kanamori's rule is also a part of this paper. Impedance spectroscopy revealed a true Warburg capacitive behaviour of the synthesized nanoplates. High magneto-electric (ME) coefficient of 27 mV cm −1 Oe −1 at a bias field of −0.2 Oe was observed which confirmed the existence of ME coupling in these nanoplates.


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