scholarly journals Defect-controlled softness, diffusive permeability, and mesh-topology of metallo-supramolecular hydrogels

Soft Matter ◽  
2022 ◽  
Author(s):  
Paola Nicolella ◽  
Martha Franziska Koziol ◽  
Lucas Löser ◽  
Kay Saalwächter ◽  
Mostafa Ahmadi ◽  
...  

In a model 4-arm pEG supramolecular network, connectivity defects are systematically introduced with different ratios of 8-arm pEG, resulting in intra-molecular loops, and providing a softer polymer network and higher self-diffusion coefficients.

Author(s):  
Д.Л. Байдаков

Методом химического нанесения из растворов халькогенидных стекол в н-бутиламине получены многокомпонентные халькогенидные пленки CuI-As2Se3, CuI-PbI2-As2Se3, CuI-SbI3-As2Se3, CuI-SbI3-PbI2-As2Se3. Синтез многокомпонентных медьсодержащих халькогенидных стекол, использовавшихся для нанесения пленок, проводили методом вакуумной плавки в кварцевых ампулах при температуре 400…950 °С и остаточном давлении не более 0,13 Па. Закалку стекол производили от 600 °С в воду со льдом с разливом расплава в ампуле. Навеску стекла размельчали в порошок и кипятили в н-бутиламине до полного растворения. Для предотвращения процессов окисления, нанесение и отжиг пленок проводили в атмосфере химически инертного азота. Подложку помещали на устройство для вращения, наносили на нее раствор и вращали подложку со скоростью несколько тысяч оборотов в минуту. Отжиг пленок проводили при температуре 100 °С в течение 1 ч. Измерение электропроводности полученных пленок проводили на постоянном и переменном токе в зависимости от значений электропроводности в температурном интервале 20…100 °С. Измерение коэффициентов диффузии проводили абсорбционным методом. Из диффузионных экспериментов определены значения коэффициентов диффузии катионов изотопа 110mAg в медьсодержащих халькогенидных пленках. Установлено, что значения коэффициентов диффузии ионов Ag+ в химически нанесенных пленках и исходных стеклах практически не различаются. Аналогию значений коэффициентов диффузии изотопа 110mAg в халькогенидных стеклах и пленках на их основе можно объяснить сохранением полимерной сетки связей халькогенидных стекол при их растворении в органических основаниях (аминах). В процессе нанесения и формирования пленок полимерная (макромолекулярная) структура раствора халькогенидных стекол сохраняется. The method of chemical deposition from solutions of chalcogenide glasses in n-butyl amine obtained multicomponent chalcogenide films CuI-As2Se3, CuI-PbI2-As2Se3, CuI-SbI3-As2Se3, CuI-SbI3-PbI2-As2Se3. Synthesis of copper multicomponent chalcogenide glasses, used for film deposition was carried out by vacuum melting in quartz ampoule at a temperature of 400…950 °C and a residual pressure of not more than 0.13 Pa. The temperature of glass produced from the 600 °C to the ice water spill of the melt in the ampoule. Weigh glass comminuted to a powder and heated in n-butylamine until complete dissolution. To prevent oxidation, deposition and annealing of the films was carried out in an atmosphere of nitrogen chemically inert. The substrate is placed on a device for rotating, it was applied to the solution and the substrate was rotated at a speed of several thousand revolutions per minute. Annealing of the films was carried out at 100 °C for 1 hour. Measurement of the electrical conductivity of the obtained films was conducted at a constant current and variable depending on the conductivity values ​​in the temperature range from 20 to 100 °C. Measurement of diffusion coefficients was performed according to the absorption method. From diffusion experiments, the values ​​of the diffusion coefficients 110mAg isotope cations in copper chalcogenide films. It was found that the values ​​of the diffusion coefficients of the ions Ag+ in a chemically deposited films and the original glasses are indistinguishable. The analogy of the diffusion coefficient values ​​110mAg isotope in chalcogenide glasses and films based on them can be attributed to the preservation of the polymer network connections chalcogenide glasses when dissolved in organic bases (amines). During application and film formation the polymer (macromolecular) structure of chalcogenide glasses of the solution is maintained.


2021 ◽  
Vol 11 (11) ◽  
pp. 5070
Author(s):  
Xesús Prieto-Blanco ◽  
Carlos Montero-Orille

In the last few years, some advances have been made in the theoretical modelling of ion exchange processes in glass. On the one hand, the equations that describe the evolution of the cation concentration were rewritten in a more rigorous manner. This was made into two theoretical frameworks. In the first one, the self-diffusion coefficients were assumed to be constant, whereas, in the second one, a more realistic cation behaviour was considered by taking into account the so-called mixed ion effect. Along with these equations, the boundary conditions for the usual ion exchange processes from molten salts, silver and copper films and metallic cathodes were accordingly established. On the other hand, the modelling of some ion exchange processes that have attracted a great deal of attention in recent years, including glass poling, electro-diffusion of multivalent metals and the formation/dissolution of silver nanoparticles, has been addressed. In such processes, the usual approximations that are made in ion exchange modelling are not always valid. An overview of the progress made and the remaining challenges in the modelling of these unique processes is provided at the end of this review.


Author(s):  
Victor P. Arkhipov ◽  
Natalia A. Kuzina ◽  
Andrei Filippov

AbstractAggregation numbers were calculated based on measurements of the self-diffusion coefficients, the effective hydrodynamic radii of micelles and aggregates of oxyethylated alkylphenols in aqueous solutions. On the assumption that the radii of spherical micelles are equal to the lengths of fully extended neonol molecules, the limiting values of aggregation numbers corresponding to spherically shaped neonol micelles were calculated. The concentration and temperature ranges under which spherical micelles of neonols are formed were determined.


Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4030
Author(s):  
Gengbiao Chen ◽  
Zhiwen Liu

The diffusion behavior of fluid water in nanochannels with hydroxylation of silica gel and silanization of different modified chain lengths was simulated by the equilibrium molecular dynamics method. The diffusion coefficient of fluid water was calculated by the Einstein method and the Green–Kubo method, so as to analyze the change rule between the modification degree of nanochannels and the diffusion coefficient of fluid water. The results showed that the diffusion coefficient of fluid water increased with the length of the modified chain. The average diffusion coefficient of fluid water in the hydroxylated nanochannels was 8.01% of the bulk water diffusion coefficient, and the diffusion coefficients of fluid water in the –(CH2)3CH3, –(CH2)7CH3, and –(CH2)11CH3 nanochannels were 44.10%, 49.72%, and 53.80% of the diffusion coefficients of bulk water, respectively. In the above four wall characteristic models, the diffusion coefficients in the z direction were smaller than those in the other directions. However, with an increase in the silylation degree, the increased self-diffusion coefficient due to the surface effect could basically offset the decreased self-diffusion coefficient owing to the scale effect. In the four nanochannels, when the local diffusion coefficient of fluid water was in the range of 8 Å close to the wall, Dz was greater than Dxy, and beyond the range of 8 Å of the wall, the Dz was smaller than Dxy.


1994 ◽  
Vol 281 ◽  
pp. 51-80 ◽  
Author(s):  
Chingyi Chang ◽  
Robert L. Powell

We study the average mobilities and long-time self-diffusion coefficients of a suspension of bimodally distributed spherical particles. Stokesian dynamics is used to calculate the particle trajectories for a monolayer of bimodal-sized spheres. Hydrodynamic forces only are considered and they are calculated using the inverse of the grand mobility matrix for far-field many-body interactions and lubrication formulae for near-field effects. We determine both the detailed microstructure (e.g. the pair-connectedness function and cluster formation) and the macroscopic properties (e.g. viscosity and self-diffusion coefficients). The flow of an ‘infinite’ suspension is simulated by considering 25, 49, 64 and 100 particles to be one ‘cell’ of a periodic array. Effects of both the size ratio and the relative fractions of the different-sized particles are examined. For the microstructures, the pair-connectedness function shows that the particles form clusters in simple shearing flow due to lubrication forces. The nearly symmetric angular structures imply the absence of normal stress differences for a suspension with purely hydrodynamic interactions between spheres. For average mobilities at infinite Péclet number, Ds0, our simulation results suggest that the reduction of Ds0 as concentration increases is directly linked to the influence of particle size distribution on the average cluster size. For long-time self-diffusion coefficients, Ds∞, we found good agreement between simulation and experiment (Leighton & Acrovos 1987 a; Phan and Leighton 1993) for monodispersed suspensions. For bimodal suspensions, the magnitude of Ds∞, and the time to reach the asymptotic diffusive behaviour depend on the cluster size formed in the system, or the viscosity of the suspension. We also consider the effect of the initial configuration by letting the spheres be both organized (size segregated) and randomly placed. We find that it takes a longer time for a suspension with an initially organized structure to achieve steady state than one with a random structure.


Sign in / Sign up

Export Citation Format

Share Document