Analyzing a fractal gel of charged oblate nanoparticles in a suspension using time-resolved rheometry and DLVO theory

2016 ◽  
Vol 186 ◽  
pp. 199-213 ◽  
Author(s):  
Shweta Jatav ◽  
Yogesh M. Joshi
Keyword(s):  
Free Energy ◽  
Fractal Dimension ◽  
Equilibrium State ◽  
Loss Tangent ◽  
Self Assembly ◽  
Dlvo Theory ◽  
Large Concentration ◽  
Time Resolved ◽  
Identical Point ◽  
Time Required

The disk-like nanoparticles of LAPONITE® are known to self-assemble to form a fractal gel within hours after a sufficiently large concentration of LAPONITE® is dispersed in water containing salt. The concentration of sodium counterions associated with LAPONITE® particles, however, continues to increase over a period of days, suggesting that delamination of LAPONITE® disks from stacks is sluggish and/or dissociation of counterions is slow. In either case, spontaneous self-assembly of LAPONITE® particles occurs even though delamination and/or counterion dissociation has not reached its equilibrium state. In order to determine the nature of the fractal gel as the extent of delamination and/or dissociation progresses towards equilibrium, we subject the LAPONITE® suspension to a freezing–defrosting cycle, which interestingly reinitiates the gelation process in suspension afresh. Application of time-resolved rheometry to a defrosted suspension shows that iso-frequency loss tangent curves intersect at an identical point, validating the Winter–Chambon criterion for a critical fractal gel state. Interestingly, while the time required to form a critical gel is observed to decrease with increased time elapsed since preparation, at which freezing–defrosting is carried out, the fractal dimension of the critical gel is observed to remain unaffected. We also solve DLVO theory for free energy interactions between the negatively charged LAPONITE® particle faces and analyze the observed phenomena.

In situ Time-Resolved Small-Angle X-ray Scattering Reveals the Formation Kinetics of Polyelectrolyte Complex Micelles

2019 ◽  
Author(s):  
Hao Wu ◽  
Jeffrey Ting ◽  
Siqi Meng ◽  
Matthew Tirrell
Keyword(s):  
Small Angle ◽  
Self Assembly ◽  
Electrostatic Interactions ◽  
Polyelectrolyte Complex ◽  
Time Resolved ◽  
X Ray ◽  
X Ray Scattering ◽  
Kinetics Of ◽  
Ray Scattering

We have directly observed the <i>in situ</i> self-assembly kinetics of polyelectrolyte complex (PEC) micelles by synchrotron time-resolved small-angle X-ray scattering, equipped with a stopped-flow device that provides millisecond temporal resolution. This work has elucidated one general kinetic pathway for the process of PEC micelle formation, which provides useful physical insights for increasing our fundamental understanding of complexation and self-assembly dynamics driven by electrostatic interactions that occur on ultrafast timescales.

scholarly journals Particle Diffusivity and Free-Energy Profiles in Hydrogels from Time-Resolved Penetration Data

2021 ◽  
Author(s):  
Amanuel Wolde-Kidan ◽  
Anna Herrmann ◽  
Albert Prause ◽  
Michael Gradzielski ◽  
Rainer Haag ◽  
...  
Keyword(s):  
Free Energy ◽  
Time Resolved ◽  
Energy Profiles ◽  
Penetration Data ◽  
Free Energy Profiles

scholarly journals Interfacial Crystallization and Supramolecular Self-Assembly of Spider Silk Inspired Protein at the Water-Air Interface

Materials ◽  
2021 ◽  
Vol 14 (15) ◽  
pp. 4239
Author(s):  
Pezhman Mohammadi ◽  
Fabian Zemke ◽  
Wolfgang Wagermaier ◽  
Markus B. Linder
Keyword(s):  
Self Assembly ◽  
Spider Silk ◽  
Assembly Process ◽  
Protein Solution ◽  
Time Resolved ◽  
Macromolecular Assembly ◽  
X Ray Scattering ◽  
Air Interface ◽  
Fundamental Research ◽  
Β Sheet

Macromolecular assembly into complex morphologies and architectural shapes is an area of fundamental research and technological innovation. In this work, we investigate the self-assembly process of recombinantly produced protein inspired by spider silk (spidroin). To elucidate the first steps of the assembly process, we examined highly concentrated and viscous pendant droplets of this protein in air. We show how the protein self-assembles and crystallizes at the water–air interface into a relatively thick and highly elastic skin. Using time-resolved in situ synchrotron X-ray scattering measurements during the drying process, we showed that the skin evolved to contain a high β-sheet amount over time. We also found that β-sheet formation strongly depended on protein concentration and relative humidity. These had a strong influence not only on the amount, but also on the ordering of these structures during the β-sheet formation process. We also showed how the skin around pendant droplets can serve as a reservoir for attaining liquid–liquid phase separation and coacervation from the dilute protein solution. Essentially, this study shows a new assembly route which could be optimized for the synthesis of new materials from a dilute protein solution and determine the properties of the final products.

Use of Minimal Free Energy and Self-Assembly To Form Shapes

1995 ◽  
Vol 7 (6) ◽  
pp. 1257-1264 ◽  
Author(s):  
Enoch Kim ◽  
George M. Whitesides
Keyword(s):  
Free Energy ◽  
Self Assembly ◽  
Minimal Free Energy

On the Existence of Multiple Equilibrium States in Strained-Layer Superlattices

1987 ◽  
Vol 103 ◽  
Author(s):  
William C. Johnson
Keyword(s):  
Free Energy ◽  
Equilibrium State ◽  
Stable Equilibrium ◽  
Multiple Equilibrium ◽  
Equilibrium Thermodynamic ◽  
Relative Thickness ◽  
Two Phase ◽  
Strained Layer ◽  
Strained Layer Superlattice ◽  
Strained Layer Superlattices

ABSTRACTUsing recent results from the thermodynamics of stressed solids, two-phase coexistence in a simple binary strained-layer superlattice is examined. We show that for a given temperature and overall composition of the superlattice, there can exist more than one linearly stable, equilibrium thermodynamic state. That is, there may exist several combinations of relative thickness of the phases and corresponding phase compositions that minimize the free energy of the system. The equilibrium state observed experimentally can, therefore, be influenced by the processing path.

In-Situ, Time Resolved, Kinetics of Reactions in Co-Ge thin Films

1991 ◽  
Vol 237 ◽  
Author(s):  
R. M. Walser ◽  
Byung-Hak Lee ◽  
Alaka Valanju ◽  
Winston Win ◽  
M. F. Becker
Keyword(s):  
Depth Profiling ◽  
Laser Interferometry ◽  
Semiconductor Interface ◽  
Time Resolved ◽  
Interface Reactions ◽  
Valuable Adjunct ◽  
Diffusion Controlled ◽  
Sputter Deposited ◽  
Time Required

ABSTRACTWe report the first kinetic study of metal-semiconductor interface reactions using in-situ, time resolved, laser interferometry. Diffusion couples with Co/Ge thicknesses of 1500 Å/1500 Å were sputter deposited on silicon wafers, and vacuum-annealed at temperatures between 300°C-400°C. Under these conditions polycrystalline CoGe was expected to form [1]. Real time laser (HeNe 6328 Å) interferograms for each anneal were recorded in-situ. These data were supplemented by information from AES and X-ray.For temperatures below 400°C the diffusion controlled formation of CoGe was observed. The composition was confirmed by Auger depth profiling that showed uniform Co and Ge concentrations when the reaction went to completion. The well defined interferences fringes were formed by the dissolution of amorphous Ge. The activation energy = 1.6 eV for the formation of CoGe were determined with precision from the temperature dependence of the time required to anneal the fixed λ/4 distance between adjacent minima and maxima of the interferogram. We discuss the evidence for formation of an intermediate Co-rich compound following the initial diffusion of Co into Ge. The results of these experiments indicate that optical interferometry will be a valuable adjunct to other techniques used to study metal-semiconductor interface reactions.

scholarly journals Surface modification and adhesion improvement of polyester films

2013 ◽  
Vol 11 (1) ◽  
pp. 35-45 ◽  
Author(s):  
Aniello Cammarano ◽  
Giovanna Luca ◽  
Eugenio Amendola
Keyword(s):  
Free Energy ◽  
Surface Modification ◽  
Surface Free Energy ◽  
Self Assembly ◽  
Treatment Time ◽  
Solution Treatment ◽  
Film Surface ◽  
Critical Surface ◽  
Hydrolysis Time ◽  
Critical Surface Tension

AbstractFacile surface modification of polyester films was performed via chemical solutions treatment. Surface hydrolysis was carried out by means of sodium hydroxide solutions, leading to the formation of carboxylate groups. Three commercial polyester films of 100 μm in thickness were used in this work: AryLite™, Mylar™, and Teonex™, hydrolysis time being the main modification parameter. FTIR-ATR analysis, topography and contact angle (CA) measurements, surface free energy (SFE) and T-Peel adhesion tests were carried out to characterize the modified films. A quantitative estimate of the carboxylates surface coverage as a function of treatment time was obtained through a supramolecular approach, i.e. the ionic self-assembly of a tetracationic porphyrin chromophore onto the film surface. The surface free energy and critical surface tension of the hydrolyzed polyesters was evaluated by means of Zisman, Saito, Berthelot and Owens-Wendt methods. It was shown that NaOH solution treatment increases roughness, polarity and surface free energy of polymers. As a result, T-Peel strengths for modified Mylar™ and Teonex™ films were respectively 2.2 and 1.8 times higher than that for the unmodified films, whereas AryLite™ adhesion test failed.

scholarly journals Two-step crystallization and solid–solid transitions in binary colloidal mixtures

2020 ◽  
Vol 117 (45) ◽  
pp. 27927-27933
Author(s):  
Huang Fang ◽  
Michael F. Hagan ◽  
W. Benjamin Rogers
Keyword(s):  
Free Energy ◽  
Self Assembly ◽  
Materials Science ◽  
Protein Structures ◽  
Free Energy Barrier ◽  
Enhanced Sampling ◽  
Homogeneous Fluid ◽  
Metastable Structures ◽  
One Step ◽  
Crystal Phases

Crystallization is fundamental to materials science and is central to a variety of applications, ranging from the fabrication of silicon wafers for microelectronics to the determination of protein structures. The basic picture is that a crystal nucleates from a homogeneous fluid by a spontaneous fluctuation that kicks the system over a single free-energy barrier. However, it is becoming apparent that nucleation is often more complicated than this simple picture and, instead, can proceed via multiple transformations of metastable structures along the pathway to the thermodynamic minimum. In this article, we observe, characterize, and model crystallization pathways using DNA-coated colloids. We use optical microscopy to investigate the crystallization of a binary colloidal mixture with single-particle resolution. We observe classical one-step pathways and nonclassical two-step pathways that proceed via a solid–solid transformation of a crystal intermediate. We also use enhanced sampling to compute the free-energy landscapes corresponding to our experiments and show that both one- and two-step pathways are driven by thermodynamics alone. Specifically, the two-step solid–solid transition is governed by a competition between two different crystal phases with free energies that depend on the crystal size. These results extend our understanding of available pathways to crystallization, by showing that size-dependent thermodynamic forces can produce pathways with multiple crystal phases that interconvert without free-energy barriers and could provide approaches to controlling the self-assembly of materials made from colloids.

scholarly journals Optically Pumped Intensive Light Amplification from a Blue Oligomer

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1534 ◽  
Author(s):  
Aljaafreh ◽  
Prasad ◽  
AlSalhi ◽  
Alahmed ◽  
M. Al-Mogren
Keyword(s):  
Self Assembly ◽  
High Efficiency ◽  
Laser Action ◽  
Pump Energy ◽  
Optically Pumped ◽  
Time Resolved ◽  
Protic Solvents ◽  
Light Amplification ◽  
Wide Range ◽  
The Fourier Transform

We demonstrated the time-resolved dynamics of laser action from the conductive oligomer (CO) 1,4-Bis(9-ethyl-3-carbazo-vinylene)-9,9-dihexyl-fluorene (BECV-DHF). Absorption and fluorescence spectra were studied for BECV-DHF in different solvents under a wide range of concentrations. The Fourier-transform infrared spectroscopy (FTIR) spectrum was measured using simulation and experiments. The Ultraviolet-Visible (UV-VIS) spectra of the BECV-DHF were simulated in two different solutions. This CO formed a dimer and had two vibration bands in nonpolar solvents, partially dissolved in polar protic solvents, and created an H-type aggregate in polar aprotic solvents. BECV-DHF produced amplified spontaneous emission (ASE) at 464 nm in many solvents. The high efficiency of ASE is due to the waveguiding and self-assembly nature of the oligomer, which is very rare for optically pumped systems. However, BECV-DHF did not produce ASE in polar protic solvents. BECV-DHF produced ASE in both longitudinal and transverse pumping, and the full-width half maximum (FWHM) was 4 nm and 8 nm respectively for different solvents, such as toluene and acetone. The CO had a very low threshold pump energy (~0.5 mJ). The ASE efficiency was approximately 20%. The time-resolved spectroscopy (TRS) studies showed a temporal Gaussian-shaped ASE output from this CO. BECV-DHF shows remarkably high stability compare to the conjugated polymer (CP) PFO-co-pX.

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