| 1. |
- Agthe, Michael, et al.
(författare)
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Controlling orientational and translational order of iron oxide nanocubes by assembly in nanofluidic containers
- 2015
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 31:45, s. 12537-12543
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate that spatial confinement can be used to control the orientational and translational order of cubic nanoparticles. For this purpose we have combined X-ray scattering and scanning electron microscopy to study the ordering of iron oxide nanocubes that have self-assembled from toluene-based dispersions in nanofluidic channels. An analysis of scattering vector components with directions parallel and perpendicular to the slit walls shows that the confining walls induce a preferential parallel alignment of the nanocube (100) faces. Moreover, slit wall separations that are commensurate with an integer multiple of the edge length of the oleic acid-capped nanocubes result in a more pronounced translational order of the self-assembled arrays compared to incommensurate confinement. These results show that the confined assembly of anisotropic nanocrystals is a promising route to nanoscale devices with tunable anisotropic properties.
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| 2. |
- Agthe, Michael, 1983-
(författare)
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Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes.We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths. We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process. We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.
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| 3. |
- Agthe, Michael, et al.
(författare)
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Dynamic growth modes of ordered arrays and mesocrystals during drop-casting of iron oxide nanocubes
- 2014
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Ingår i: CrystEngComm. - : Royal Society of Chemistry (RSC). - 1466-8033. ; 16:8, s. 1443-1450
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Tidskriftsartikel (refereegranskat)abstract
- The growth modes of self-assembled mesocrystals and ordered arrays from dispersions of iron oxide nanocubes with a mean edge length of 9.6 nm during controlled solvent removal have been investigated with a combination of visible light video microscopy, atomic force microscopy and scanning electron microscopy. Mesocrystals with translational and orientational order of sizes up to 10 mu m are formed spontaneously during the final, diffusion-controlled, drop-casting stage when the liquid film is very thin and the particle concentration is high. Convection-driven deposition of ordered nanocube arrays at the edge of the drying droplet is a manifestation of the so called coffee-ring effect. Dendritic growth or fingering of rapidly growing arrays of ordered nanocubes could also be observed in a transition regime as the growth front moves from the initial three-phase contact line towards the centre of the original droplet.
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| 4. |
- Agthe, Michael, et al.
(författare)
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Following in Real Time the Two-Step Assembly of Nanoparticles into Mesocrystals in Levitating Drops
- 2016
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Ingår i: Nano Letters. - : American Chemical Society (ACS). - 1530-6984 .- 1530-6992. ; 16:11, s. 6838-6843
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Tidskriftsartikel (refereegranskat)abstract
- Mesocrystals composed of crystallographically aligned nanocrystals are present in biominerals and assembled materials which show strongly directional properties of importance for mechanical protection and functional devices. Mesocrystals are commonly formed by complex biomineralization processes and can also be generated by assembly of anisotropic nanocrystals. Here, we follow the evaporation-induced assembly of maghemite nanocubes into mesocrystals in real time in levitating drops. Analysis of time-resolved small-angle X-ray scattering data and ex situ scanning electron microscopy together with interparticle potential calculations show that the substrate-free, particle-mediated crystallization process proceeds in two stages involving the formation and rapid transformation of a dense, structurally disordered phase into ordered mesocrystals. Controlling and tailoring the particle-mediated formation of mesocrystals could be utilized to assemble designed nanoparticles into new materials with unique functions.
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| 5. |
- Agthe, Michael, et al.
(författare)
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Following the Assembly of Iron Oxide Nanocubes by Video Microscopy and Quartz Crystal Microbalance with Dissipation Monitoring
- 2017
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 33:1, s. 303-310
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the growth of ordered arrays by evaporation-induced self-assembly of iron oxide nanocubes with edge lengths of 6.8 and 10.1 nm using video microscopy (VM) and quartz crystal microbalance with dissipation monitoring (QCM-D). Ex situ electron diffraction of the ordered arrays demonstrates that the crystal axes of the nanocubes are coaligned and confirms that the ordered arrays are mesocrystals. Time-resolved video microscopy shows that growth of the highly ordered arrays at slow solvent evaporation is controlled by particle diffusion and can be described by a simple growth model. The growth of each mesocrystal depends only on the number of nanoparticles within the accessible region irrespective of the relative time of formation. The mass of the dried mesocrystals estimated from the analysis of the bandwidth-shift-to-frequency-shift ratio correlates well with the total mass of the oleate-coated nanoparticles in the deposited dispersion drop.
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| 6. |
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| 7. |
- Guccini, Valentina, et al.
(författare)
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Inducing nematic ordering of cellulose nanofibers using osmotic dehydration
- 2018
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Ingår i: Nanoscale. - : Royal Society of Chemistry. - 2040-3364 .- 2040-3372. ; 10:48, s. 23157-23163
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Tidskriftsartikel (refereegranskat)abstract
- The formation of nematically-ordered cellulose nanofiber (CNF) suspensions with an order parameter fmax ≈ 0.8 is studied by polarized optical microscopy, small-angle X-ray scattering (SAXS), and rheological measurements as a function of CNF concentration. The wide range of CNF concentrations, from 0.5 wt% to 4.9 wt%, is obtained using osmotic dehydration. The rheological measurements show a strong entangled network over all the concentration range whereas SAXS measurements indicate that at concentrations >1.05 wt% the CNF suspension crosses an isotropic-anisotropic transition that is accompanied by a dramatic increase of the optical birefringence. The resulting nanostructures are modelled as mass fractal structures that converge into co-existing nematically-ordered regions and network-like regions where the correlation distances decrease with concentration. The use of rapid, upscalable osmotic dehydration is an effective method to increase the concentration of CNF suspensions while partly circumventing the gel/glass formation. The facile formation of highly ordered fibers can result in materials with interesting macroscopic properties.
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| 8. |
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| 9. |
- Kapuscinski, Martin, et al.
(författare)
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Temporal Evolution of Superlattice Contraction and Defect-Induced Strain Anisotropy in Mesocrystals during Nanocube Self-Assembly
- 2020
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 14:5, s. 5337-5347
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Tidskriftsartikel (refereegranskat)abstract
- Understanding and controlling defect formation during the assembly of nanoparticles is crucial for fabrication of self-assembled nanostructured materials with predictable properties. Here, time-resolved small-angle X-ray scattering was used to probe the temporal evolution of strain and lattice contraction during evaporation-induced self-assembly of oleate-capped iron oxide nanocubes in a levitating drop. We show that the evolution of the strain and structure of the growing mesocrystals is related to the formation of defects as the solvent evaporated and the assembly process progressed. Superlattice contraction during the mesocrystal growth stage is responsible for the rapidly increasing isotropic strain and the introduction of point defects. The crystal strain, quantified by the Williamson-Hall analysis, became more anisotropic due to the formation of stress-relieving dislocations as the mesocrystal growth was approaching completion. Understanding the formation of the transformation of defects in mesocrystals and superlattices could assist in the development of optimized assembly processes of nanoparticles with multifunctional properties.
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| 10. |
- Kapuscinski, Martin, et al.
(författare)
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Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring
- 2018
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 522, s. 104-110
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Tidskriftsartikel (refereegranskat)abstract
- Self-assembly of nanoparticles into superlattices can be used to create hierarchically structured materials with tailored functions. We have used the surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) technique in combination with video microscopy (VM) to obtain time-resolved information on the mass increase and rheological properties of evaporation-induced self-assembly of nanocubes. We have recorded the frequency and dissipation shifts during growth and densification of superlattices formed by self-assembly of oleic acid capped, truncated iron oxide nanocubes and analyzed the time-resolved QCM-D data using a Kelvin-Voigt viscoelastic model. We show that the nanoparticles first assemble into solvent-containing arrays dominated by a viscous response followed by a solvent releasing step that results in the formation of rigid and well-ordered superlattices. Our findings demonstrate that QCM-D can be successfully used to follow self-assembly and assist in the design of optimized routes to produce well-ordered superlattices.
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