scholarly journals Water Clusterization in the Interparticle Space of Hydrophobic Nanosilica АМ-1

2021 ◽  
Vol 22 (1) ◽  
pp. 24-30
Author(s):  
T.V. Krupskaya ◽  
V. M. Gun’ko ◽  
L.S. Andriyko ◽  
N.V. Yelahina ◽  
V.V. Turov

The processes occurring in hydrated powders and concentrated suspensions of hydrophobic silica were studied by 1H NMR spectroscopy. It is shown that a mixture of methyl silica and water with a hydration of less than 1 g / g is a wet powder, where water is in the form of submicron clusters filling the interparticle voids of nanosilica, and the interfacial energy is directly proportional to the amount of added water. It was found that at high water concentrations there is a spontaneous increase in the size of water structures, which is accompanied by a sharp decrease in interfacial energy, that may reflect the disappearance of narrow interparticle voids or their filling with air. It is shown that aqueous suspensions of AM-1 are easily mixed with a weakly polar organic solvent chloroform, forming a stable suspension with close the amounts both of water and chloroform. It was revealed that the aqueous suspension of methyl silica has high thixotropic properties, which depend on the time and the magnitude of the applied mechanical loads.

Author(s):  
Vladimir V. Turov ◽  
◽  
Tetyana V. Krupska ◽  
Vladimir M. Gun'ko ◽  
Mykola T. Kartel ◽  
...  

In order to study the peculiarities of the interaction of hydrophobic particles with water, the binding of water in composite systems based on structurally modified mixtures of 1/1 hydrophilic (A-300) and hydrophobic (AM-1-300) silica was studied by low-temperature 1H NMR spectroscopy. It is shown that with equal amounts of hydrophobic and hydrophilic components, the dependence of the interfacial energy on the value of surface hydration has a bell-shaped appearance with a maximum at h = 3000 mg/g. The obtained dependence is explained from the point of view of restructuring of the composite system under the influence of mechanical loads and the possibility of air removal and adsorption processes in the interparticle gaps of hydrophobic and hydrophilic components, as well as the phenomenon of nanocoagulation. Increasing the concentration of the hydrophilic component does not increase the binding energy of water. Under the influence of liquid hydrophobic substances, depending on the bulk density of the composite, there may be an increase or decrease in interfacial energy. The growth is due to the restructuring of the hydrophobic and hydrophilic components (nanocoagulation), and the decrease is due to the displacement of water from the surface into pores of larger radius. For n-decane, the effect of increasing the melting temperature by several tens of degrees was registered in the interparticle gaps.


Materials ◽  
2020 ◽  
Vol 13 (23) ◽  
pp. 5494
Author(s):  
João A. O. Santos ◽  
Alessandra M. G. Mutti ◽  
Airton G. Bispo-Jr ◽  
Ana M. Pires ◽  
Sergio A. M. Lima

Luminescent organic-inorganic hybrids containing lanthanides (Ln3+) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO2) nanospheres decorated with Eu3+ β–diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO2 surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu3+ to the carboxylate groups and (iv) coordination of dbm− to Eu3+. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu3+-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of −27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu3+ complex provides intense red luminescence, characteristic of Eu3+5D0→7FJ electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging.


Surface ◽  
2020 ◽  
Vol 12(27) ◽  
pp. 100-136
Author(s):  
T. V. Krupska ◽  
◽  
V. M. Gun'ko ◽  
I. S. Protsak ◽  
I. I. Gerashchenko ◽  
...  

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.


2020 ◽  
pp. 303-314
Author(s):  
Ol'ga Vladimirovna Yatsenkova ◽  
Andrey Mikhaylovich Skripnikov ◽  
Anton Aleksandrovich Karacharov ◽  
Elena Valentinovna Mazurova ◽  
Sergey Aleksandrovich Vorob'yev ◽  
...  

The new method of producing of microfibrillated cellulose (MFC) from spruce wood was described. This method includes the stages of cellulose obtaining by peroxide delignification of wood in the medium “acetic acid-water-H2SO4 catalyst” and cellulose acid hydrolysis, ultrasonic treatment, and freeze drying. The structure of cellulosic products was studied by FTIR, XRD, SEM, AFM, dynamic light scattering methods. The particle size of final cellulosic products is characteristic of microfibrillated cellulose according to the TAPPI Standard WI 3021 classification. The particles of the MFC are characterized by a rather high surface charge, and its aqueous suspension showed a high colloidal stability for a long time. According to the AFM data the surface of the microfibrillated cellulose film is formed by homogeneous spherical particles with a diameter about 80 nm and does not contain external inclusions. The new method of obtaining MFC from spruce wood is less energy-consuming and more environmentally friendly compared to traditional technologies due to single-stage production of high quality cellulose without the use of sulfur- and chlorine containing delignifying agents, increased pressure and high water consumption.


2005 ◽  
Vol 495-497 ◽  
pp. 63-68
Author(s):  
F. Heidelbach ◽  
B. Holtzman ◽  
S. Hier-Majumder ◽  
D. Kohlstedt

The texture development in experimentally sheared aggregates of olivine was monitored as a function of increased water content and added melt. In dry samples, an alignment of {010} with the shear plane and <100> and <001> with the shear direction, respectively, was observed, consistent with intracrystalline glide on the (010)[100] and (010)[001] slip systems. Samples with high water content showed consistently stronger textures of the (010)[100] component for comparable shear strains indicating that water may especially ease glide on this slip system. Samples with added melt showed an increased alignment of {010} and <001> subparallel to shear plane and shear direction respectively, whereby the maxima were consistently rotated 10 to 20° against the sense of shear. This type of texture can be explained by a combination of increased glide on the (010)[001] slip system in combination with a partitioning of the strain between melt rich bands and relatively melt free regions in the sample. Physical anisotropies calculated from the textures indicate that increased water content causes enhanced anisotropy for longitudinal and transverse seismic waves. The addition of melt on the other hand may change the type of anisotropy that develops during deformation, but does not significantly change the magnitude of anisotropy compared to samples of pure olivine.


Surface ◽  
2020 ◽  
Vol 12(27) ◽  
pp. 53-99
Author(s):  
V. V. Turov ◽  
◽  
V. M. Gun’ko ◽  
T. V. Krupskaya ◽  
I. S. Protsak ◽  
...  

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.


2020 ◽  
Vol 21 (1) ◽  
pp. 132-139
Author(s):  
V. V. Turov ◽  
I. I. Gerashchenko ◽  
T. V. Krupskaya ◽  
N. Yu. Klymenko ◽  
K. O. Stepanuk

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.


Author(s):  
Martin A. Levin ◽  
Lisa L. Cale ◽  
Valerie Lynch-Holm

Orchestia is a genus of amphipod in the crustacean class Malacostraca. The order Amphipoda contains over 6000 species commonly called side swimmers, scuds and beach fleas(1). Most are marine bottom-dwellers utilizing their thoracic legs and posterior abdominal uropods for walking, crawling and swimming. However, some, like those in the genera Orchestia and Hyale are semiterrestrial. These amphipods, commonly referred to as “beach fleas,' “beach hoppers” or “sand fleas” can hop vigorously for great distances (up to 50 times their length) by extending their abdomens and telsons against the sand(2).In our study, the ultrastructure of the dorsal muscle cord of Orchestia grillus was examined. Vogel(3) described the abdominal muscles of Orchestia cavimana as consisting of two groups of muscles: a strong, complex, dorsal muscle cord used mainly for hopping and a group of weaker, ventral, longitudinal and oblique muscles.The specimens were collected in clumps of decaying seaweed and other detritus from the intertidal zone near the high water mark at Avery Point Beach, Connecticut.


Author(s):  
H. Mori ◽  
Y. Murata ◽  
H. Yoneyama ◽  
H. Fujita

Recently, a new sort of nano-composites has been prepared by incorporating such fine particles as metal oxide microcrystallites and organic polymers into the interlayer space of montmorillonite. Owing to their extremely large specific surface area, the nano-composites are finding wide application[1∼3]. However, the topographic features of the microstructures have not been elucidated as yet In the present work, the microstructures of iron oxide-pillared montmorillonite have been investigated by high-resolution transmission electron microscopy.Iron oxide-pillared montmorillonite was prepared through the procedure essentially the same as that reported by Yamanaka et al. Firstly, 0.125 M aqueous solution of trinuclear acetato-hydroxo iron(III) nitrate, [Fe3(OCOCH3)7 OH.2H2O]NO3, was prepared and then the solution was mixed with an aqueous suspension of 1 wt% clay by continuously stirring at 308 K. The final volume ratio of the latter aqueous solution to the former was 0.4. The clay used was sodium montmorillonite (Kunimine Industrial Co.), having a cation exchange capacity of 100 mequiv/100g. The montmorillonite in the mixed suspension was then centrifuged, followed by washing with deionized water. The washed samples were spread on glass plates, air dried, and then annealed at 673 K for 72 ks in air. The resultant film products were approximately 20 μm in thickness and brown in color.


1965 ◽  
Vol 8 (3) ◽  
pp. 245-251 ◽  
Author(s):  
Gerald M. Siegel ◽  
Richard R. Martin

Forty normal speakers were divided into two groups to study the effects of two types of verbal punishment of disfluencies. The two conditions, Random and Contingent, were divided into three segments each. Punishment was not delivered in Segments 1 or 3. Segment 2 presented Random subjects with the tape recorded word “wrong” on a predetermined random schedule. Contingent subjects were delivered the word “wrong” after each disfluency. Random presentation of “wrong” did not significantly affect rate of disfluencies. Contingent presentation resulted in a sharp decrease in disfluencies during Segment 2, and an increase in disfluencies during Segment 3.


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