Use of microcoagulation effect to control water binding in a heterogeneous polymethylsiloxane/silica/water system

The binding of water in heterogeneous systems containing polymethylsiloxane (PMS) pyrogenic nanosilica (A-300) water and the surface-active substance decametoxin (DMT) was studied. Composite systems were created using metered mechanical loads. The low-temperature 1H NMR spectroscopy was used to measure the structural and thermodynamic parameters of bound water. It is shown that when filling PMS interparticle gaps with hydrocompaction, the interfacial energy of water in the interparticle gaps of hydrophobic PMS with the same hydration is twice as large as the interfacial energy of water in hydrophilic silica A-300. This is due to the smaller linear dimensions of the interparticle gaps in the ICP compared with the A-300. In the composite system, A-300/PMS/DMT/H2O, a non-additive growth of water binding energy is observed, which is likely due to the formation, under the influence of mechanical load in the presence of water, of microheterogeneous sites, consisting mainly of the hydrophobic and hydrophilic components (microcoagulation). Thus, using mechanical loads, you can control the adsorption properties of composite systems.

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Properties of composite systems based on polymethylsiloxane and silica in the water environment

Surface ◽

10.15407/surface.2020.12.100 ◽

2020 ◽

Vol 12(27) ◽

pp. 100-136

Author(s):

T. V. Krupska ◽

◽

V. M. Gun'ko ◽

I. S. Protsak ◽

I. I. Gerashchenko ◽

...

Keyword(s):

Interfacial Energy ◽

Composite System ◽

Close Contact ◽

Water Environment ◽

Heterogeneous Systems ◽

Adsorption Properties ◽

Mechanical Loads ◽

Composite Systems ◽

System A ◽

Hydrophilic Particles

The formation of a composite system based on equal amounts of hydrophobic, porous polymethylsiloxane and hydrophilic nanosilicon A-300 was studied. It is shown that during the formation of a composite system the specific surface of the material is significantly reduced, which is due to the close contact between hydrophobic and hydrophilic particles. When water is added to the composite system, in the process of homogenization under conditions of dosed mechanical loading, the effect of nanocoagulation is manifested – the formation of nanosized particles of hydrated silica inside the polymethylsiloxane matrix, recorded on TEM microphotographs. When measuring the value of the interfacial energy of PMS and PMS/A-300 composite by low-temperature 1H NMR spectroscopy, it was found that the effect of nanocoagulation is manifested in a decrease (compared to the original PMS) energy of water interaction with the surface of the composite obtained under small mechanical conditions. its growth when using high mechanical loads. In the process, the binding of water in heterogeneous systems containing PMS, pyrogenic nanosilica (A-300), water and surfactants – decamethoxine (DMT) was studied. Composite systems were created using metered mechanical loads. It is shown that when filling the interparticle gaps of PMS by the method of hydrosealing, the interphase energy of water in the interparticle gaps of hydrophobic PMS with the same hydration is twice the interfacial energy of water in hydrophilic silica A-300. This is due to the smaller linear dimensions of the interparticle gaps in PMS compared to A-300. In the composite system, A-300/PMS/DMT/H2O there are non-additive growth of binding energy of water, which is probably due to the formation, under the influence of mechanical stress in the presence of water, microheterogeneous areas consisting mainly of hydrophobic and hydrophilic components (microcoagulation). Thus, with the help of mechanical loads, you can control the adsorption properties of composite systems and create new materials with unique adsorption properties.

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Interphase interactions of hydrophobic powders based on methilsilica in the water environment

Surface ◽

10.15407/surface.2020.12.053 ◽

2020 ◽

Vol 12(27) ◽

pp. 53-99

Author(s):

V. V. Turov ◽

◽

V. M. Gun’ko ◽

T. V. Krupskaya ◽

I. S. Protsak ◽

...

Keyword(s):

Interfacial Energy ◽

Water Environment ◽

Heterogeneous Systems ◽

Stable State ◽

Water System ◽

Water Concentration ◽

Binding Energies ◽

Concentrated Suspension ◽

Mechanical Loads ◽

Hydrophobic Silica

Using modern physicochemical research methods and quantum chemical modeling, the surface structure, morphological and adsorption characteristics, phase transitions in heterogeneous systems based on methylsilica and its mixtures with hydrophilic silica were studied. It is established that at certain concentrations of interfacial water, hydrophobic silica or their composites with hydrophilic silica form thermodynamically unstable systems in which energy dissipation can be carried out under the influence of external factors: increasing water concentration, mechanical loads and adsorption of air by hydrophobic component. When comparing the binding energies of water in wet powders of wettind-drying samples A-300 and AM-1, which had close values of bulk density (1 g/cm3) and humidity (1 g/g), close to 8 J/g. However, the hydration process of hydrophobic silica is accompanied by a decrease in entropy and the transition of the adsorbent-water system to a thermodynamically nonequilibrium state, which is easily fixed on the dependences of interfacial energy (S) on the amount of water in the system (h). It turned out that for pure AM-1 the interfacial energy of water increases in proportion to its amount in the interparticle gaps only in the case when h < 1 g/g. With more water, the binding energy decreases abruptly, indicating the transition of the system to a more stable state, which is characterized by the consolidation of clusters of adsorbed water and even the formation of a bulk phase of water. Probably there is a partial "collapse" of the interparticle gaps of hydrophobic particles AM-1 and the release of thermodynamically excess water. For mixtures of hydrophobic and hydrophilic silica, the maximum binding of water is shifted towards greater hydration. At AM1/A-300 = 1/1 the maximum is observed at h = 3g/g, and in the case of AM1/A-300 = 1/2 it is not reached even at h = 4 g/g. The study of the rheological properties of composite systems has shown that under the action of mechanical loads, the viscosity of systems decreases by almost an order of magnitude. However, after withstanding the load and then reducing the load to zero, the viscosity of the system increases again and becomes significantly higher than at the beginning of the study. That is, the obtained materials have high thixotropic properties. Thus, a wet powder that has all the characteristics of a solid after a slight mechanical impact is easily converted into a concentrated suspension with obvious signs of liquid.

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Composite systems for medical purposes, created on the basis of hydrophobic silica

Surface ◽

10.15407/surface.2021.13.246 ◽

2021 ◽

Vol 13(28) ◽

pp. 246-275

Author(s):

V. V. Turov ◽

◽

P. P. Gorbyk ◽

T. V. Krupska ◽

S. P. Turanska ◽

...

Keyword(s):

Bound Water ◽

Adsorbed Water ◽

Strong Acid ◽

Acid Media ◽

Water Binding ◽

Composite Systems ◽

Hydrophobic Materials ◽

Protein Molecules ◽

Hydrophobic Component ◽

Different Order

Composite systems with certain cytotoxic (AM1/lectin) and adsorption (AM1/gelatin) activity have been developed on the basis of methyl silica and protein molecules – lectin and gelatin. For both types of composites, mechanisms of water binding to the surface and methods of transferring of hydrophobic materials into the aquatic environment have been investigated. The state of interfacial water in air, organic and acid media was studied. It has been found that the presence of a hydrophobic component in composites stabilizes of surface water in a weakly associated state, when a significant part of water molecules does not form hydrogen bonds. Liquid hydrophobic medium enhances this effect, and the strong acid (trifluoroacetic), added to it, promotes the transition of water to a strongly associated state. It has been shown that the redistribution of water in the interparticle intervals of AM1 with protein molecules immobilized on their surface changes under the influence of mechanical loads. Mechanoactivated samples are characterized by the possibility of water penetration into the spaces between the primary particles of methyl silica. It has been shown that immobilization of lectin on the surface of AM1 is accompanied by an increase in the interfacial energy gS from 4.1 to 5.2 J/g. This is due to an increase in the concentration of strongly bound water. If we analyze the changes in the distributions of radii R of the clusters of adsorbed water, we can state that in the water adsorbed by native lectin molecules, there are two main maxima at R = 1 and 3 nm. In the immobilized state, the maximum at R = 1 nm is present in both types of water (of different order), but the second maximum is observed only for more ordered associates.

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