Interfacial phenomena at a surface of individual and complex fumed nanooxides.

Investigations of interfacial and temperature behaviors of nonpolar and polar adsorbates interacting with individual and complex fumed metal or metalloid oxides (FMO), initial and subjected to various treatments or chemical functionalization and compared to such porous adsorbents as silica gels, precipitated silica, mesoporous ordered silicas, filled polymeric composites, were analyzed. Complex nanooxides include core-shell nanoparticles, CSNP (50-200nm in size) with titania or alumina cores and silica or alumina shells in contrast to simple and smaller nanoparticles of individual FMO. CSNP could be destroyed under high-pressure cryogelation (HPCG) or mechanochemical activation (MCA). These treatments affect the structure of aggregates of nanoparticles and agglomerates of aggregates, resulting in their becoming more compacted. The analysis shows that complex FMO could be more sensitive to external actions than simple nanooxides such as fumed silica. Any treatment of 'soft' FMO affects the interfacial and temperature behaviors of polar and nonpolar adsorbates. Rearrangement of secondary particles and surface functionalization affects the freezing-melting point depression of adsorbates. For some adsorbates, open hysteresis loops became readily apparent in adsorption-desorption isotherms. Clustering of adsorbates bound in textural pores in aggregates of nanoparticles (i.e., voids between nanoparticles in secondary structures) causes reduced changes in enthalpy during phase transitions (freezing, fusion, evaporation). Freezing point depression and melting point elevation cause significant hysteresis freezing-melting effects for adsorbates bound to FMO in the textural pores. Relaxation phenomena for both low- and high-molecular weight adsorbates or filled polymeric composites are affected by the morphology of primary particles, structural organization of secondary particles of differently treated or functionalized FMO, content of adsorbates, co-adsorption order, and temperature.

Interfacial behavior of polar, weakly polar, and nonpolar compounds bound to activated carbons.

Detailed analysis of the interfacial behavior of water and weakly polar or nonpolar organics adsorbed alone or co-adsorbed onto activated carbons (AC) at different temperatures is a complex problem important for practical applications of adsorbents. Interaction of water, 1-decanol, and n-decane with AC possessing highly developed porosity (pore volume Vp≈1.4-2.3 cm(3)/g, specific surface area S(BET)≈1500-3500 m(2)/g) was studied over a broad temperature range using differential scanning calorimetry (DSC), thermoporometry, (1)H NMR spectroscopy, cryoporometry, and temperature-programmed desorption with mass-spectrometry control methods. Comparison of the pore size distributions (PSD) calculated using the DSC thermoporometry, NMR cryoporometry, and nitrogen adsorption isotherms allows us to determine localization of adsorbates in different pores, as well as changes in the PSD of AC due to freezing of adsorbates in pores. Theoretical calculations (using ab initio HF/6-31G(d,p), DFT B3LYP/6-31G(d,p), and PM7 methods) explain certain aspects of the interfacial behavior of water, decane, and decanol adsorbed onto AC that appear in the experimental data. Obtained results show strong temperature dependence (above and below the freezing point, Tf, of bulk liquids) of the interfacial behavior of adsorbates on the textural characteristics and hydrophilic/hydrophobic properties of AC and the adsorbate amounts that affect the distributions of adsorbates unfrozen at T

Adsorption of polar and nonpolar compounds onto complex nanooxides with silica, alumina, and titania.

Adsorption of low-molecular adsorbates (nonpolar hexane, nitrogen, weakly polar acetonitrile, and polar diethylamine, triethylamine, and water) onto individual (silica, alumina, titania), binary (silica/alumina (SA), silica/titania (ST)), and ternary (alumina/silica/titania, AST) fumed oxides was studied to analyse the effects of morphology and surface composition of the materials. Certain aspects of the interfacial phenomena dependent on the structural characteristics of oxides were analysed using calorimetry, (1)H NMR, and Raman spectroscopies, XRD, and ab initio quantum-chemical calculations. The specific surface area S(BET,X)-to-S(BET,N(2)) ratio (X is an organic adsorbate) changes from 0.68 for hexane adsorbed onto amorphous SA8 (degassed at 200 degrees C) to 1.85 for acetonitrile adsorbed onto crystalline alumina (degassed at 900 degrees C). These changes are relatively large because of variations in orientation, lateral interactions, and adsorption compressing of molecules adsorbed onto oxide surfaces. Larger S(BET,X)/S(BET,N(2)) values are observed for mixed oxides with higher crystallinity of titania or/and alumina phases in larger primary nanoparticles with greater surface roughness and hydrophilicity. Polar adsorbates can change the structure of aggregates of oxide nanoparticles that can, in turn, affect the results of adsorption measurements.

Well-defined oxide core-polymer shell nanoparticles: interfacial interactions, peculiar dynamics, and transitions in polymer nanolayers.

Interfacial interactions, chain dynamics, and glass and melting transitions were studied in well-defined core-shell nanoparticles with amorphous silica or crystalline alumina cores and noncrystallizable poly(vinyl pyrrolidone) (PVP) or crystallizable poly(ethylene glycol) (PEG) shells. Varying particle composition caused regular changes in the shell thickness from 1 to 2 nm (monomolecular layer) up to 90 nm. Far- and mid-IR spectroscopy allowed us to register hydrogen bonding and, tentatively, Lewis/Brønsted (LB) interfacial interactions as well as changes in the dynamics and conformational state of the polymer chains as a function of the nanoshell thickness. Their most pronounced peculiarities were found for the monomolecular polymer layers. The LB interactions were stronger with the alumina substrate than silica. DSC analysis was performed, and the data obtained were in agreement with the spectroscopic data. Unlike the bulk polymer, the PVP monolayer was characterized with an extraordinarily large dynamic heterogeneity within the glass transition while broadening the transition range and varying the activation energy by an order of magnitude. The PEG monolayer adsorbed on silica was totally amorphous, whereas a highly crystalline one with the anomalously thin lamellae, down to 3 nm thick, was adsorbed on an alumina surface, presumably as a result of the quasi-heteroepitaxial crystallization process.

Structural and adsorption characteristics and catalytic activity of titania and titania-containing nanomaterials.

Morphological, structural, adsorption, and catalytic properties of highly disperse titania prepared using sulfate and pyrogenic methods, and fumed titania-containing mixed oxides, were studied using XRD, TG/DTA, nitrogen adsorption, (1)H NMR, FTIR, microcalorimetry on immersion of oxides in water and decane, thermally stimulated depolarization current (TSDC) and catalytic photodecomposition of methylene blue (MB). Phase composition and aggregation characteristics of nanoparticles (pore size distribution) of sulfate and pyrogenically prepared titania are very different; temperature dependent structural properties are thus very different. Catalytic activity for the photodecomposition of MB is greatest (per gram of TiO(2) for the pure oxide materials) for non-treated ultrafine titania PC-500, which has the largest S(BET) value and smallest particle size of the materials studied. However, this activity calculated per m(2) is higher for PC-105, possessing a much smaller S(BET) value than PC-500. The activity per unit surface area of titania is greatest for the fumed silica-titania mixed oxide ST20. Calcination of PC-500 at 650 degrees C leads to enhancement of anatase content and catalytic activity, but heating at 800 and 900 degrees C lowers the anatase content (since rutile appears) and diminishes catalytic activity, as well as the specific surface area because of nanoparticle sintering.

Structural features of polymer adsorbent LiChrolut EN and interfacial behavior of water and water/organic mixtures.

The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data.

Surface structure and properties of mixed fumed oxides.

A variety of fumed oxides such as silica, alumina, titania, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST) were characterized. These oxides have different specific surface areas and different primary particle composition in the bulk and at the surface. These materials were studied by FTIR, NMR, Auger electron spectroscopy, one-pass temperature-programmed desorption with mass spectrometry control (OP TPDMS), microcalorimetry, and nitrogen adsorption. Nonlinear changes in the surface content of alumina in SA and AST and titania in ST and AST samples with increasing oxide content along with simultaneous changes in their specific surface area cause complex dependencies of the heat of immersion in water and desorption of water on heating on the structural parameters. Simultaneous analysis of changes in the surface phase composition, in the concentration of hydroxyls, and in the structural characteristics reveals that at a low content of the second phase the structural characteristics (e.g., S(BET)) are predominant; however, at a large content of these oxides the phase composition plays a more important role.

Relaxation phenomena in poly(vinyl alcohol)/fumed silica affected by interfacial water.

Interaction of poly(vinyl alcohol) (PVA) with fumed silica was investigated in the gas phase and aqueous media using adsorption, broadband dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization current (TSDC), infrared spectroscopy, thermal analysis, and one-pass temperature-programmed desorption (OPTPD) mass-spectrometry (MS) methods. PVA monolayer formation leads to certain textural changes in the system (after suspension and drying) because of strong hydrogen bonding of the polymer molecules to silica nanoparticles preventing strong interaction between silica particles themselves. This strong interaction promotes associative desorption of water molecules at lower temperatures than in the case of silica alone. Interaction of PVA with silica and residual water leads to depression of glass transition temperature (T(g)). There are three types of dipolar relaxations at temperatures lower and higher than the T(g) value. A small amount of adsorbed water leads to significant conductivity with elevating temperature.

Adsorption, NMR, and thermally stimulated depolarization current methods for comparative analysis of heterogeneous solid and soft materials.

Structural characterization of different silicas (ordered mesoporous silicas MCM-41, MCM-48, and SBA-15, amorphous silica gels Si-40, Si-60, and Si-100, and initial and wetted-dried fumed silica A-300) and bio-objects (fibrinogen solution, yeast cells, wheat seeds, and bone tissues) has been done using two versions of cryoporometry based on integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids measured by 1H NMR spectroscopy (180-200 < T < 273 K) and thermally stimulated depolarization current (TSDC) method (90 < T < 273 K). The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Comparison of the PSDs calculated by using the cryoporometry and nitrogen adsorption methods for the mentioned silicas demonstrates that IGT equation provides satisfactory fit which is better than that obtained with nonintegral Gibbs-Thomson (GT) equation (based on the GT equation) proposed by Aksnes and Kimtys. The NMR- and TSDC-cryoporometry methods applied to probe biosystems give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and human bone tissue disease.

Comparative characterization of polymethylsiloxane hydrogel and silylated fumed silica and silica gel.

Polymethylsiloxane (PMS) hydrogel (C(PMS)=10 wt%, soft paste-like hydrogel), diluted aqueous suspensions, and dried/wetted xerogel (powder) were studied in comparison with suspensions and dry powders of unmodified and silylated nanosilicas and silica gels using (1)H NMR, thermally stimulated depolarization current (TSDC), quasielastic light scattering (QELS), rheometry, and adsorption methods. Nanosized primary PMS particles, which are softer and less dense than silica ones because of the presence of CH(3) groups attached to each Si atom and residual silanols, form soft secondary particles (soft paste-like hydrogel) that can be completely decomposed to nanoparticles with sizes smaller than 10 nm on sonication of the aqueous suspensions. Despite the soft character of the secondary particles, the aqueous suspensions of PMS are characterized by a higher viscosity (at concentration C(PMS)=3-5 wt%) than the suspension of fumed silica at a higher concentration. Three types of structured water are observed in dry PMS xerogel (adsorbed water of 3 wt%). These structures, characterized by the chemical shift of the proton resonance at delta(H) approximately 1.7,3.7, and 5 ppm, correspond to weakly associated but strongly bound water and to strongly associated but weakly or strongly bound waters, respectively. NMR cryoporometry and QELS results suggest that PMS is a mesoporous-macroporous material with the textural porosity caused by voids between primary particles forming aggregates and agglomerates of aggregates. PMS is characterized by a much smaller adsorption capacity with respect to proteins (gelatin, ovalbumin) than unmodified fumed silica A-300.

TSDC spectroscopy of relaxational and interfacial phenomena.

Applications of thermally stimulated depolarisation current (TSDC) technique to a variety of systems with different dispersion phases such as disperse and porous metal oxides, polymers, liquid crystals, amorphous and crystalline solids, composites, solid solutions, biomacromolecules, cells, tissues, etc. in gaseous or liquid dispersion media are analysed. The effects of dipolar, direct current (dc) and space charge relaxations are linked to the temperature dependent mobility of molecules, their fragments, protons, anions, and electrons and depend on thermal treatment, temperature and field intensity of polarisation, heating rate on depolarisation or cooling rate on polarisation. Features of the relaxation mechanisms are affected not only by the mentioned factors but also by morphological, structural and chemical characteristics of materials. The interfacial phenomena, especially the role of interfacial water, received significant attention on analysis of the TSDC data. Comparison of the data of TSDC and dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC), 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial water, adsorption/desorption of nitrogen, water and dissolved organics demonstrates high sensitivity and information content of the TSDC technique, allowing a deeper understanding of interfacial phenomena.

Successive interaction of pairs of soluble organics with nanosilica in aqueous media.

Successive interaction of different pairs of water-soluble polymers (poly(ethylene glycol) (PEG), poly(vinyl pyrrolidone) (PVP), poly(vinyl alcohol) (PVA)), proteins (bovine serum albumin (BSA), ovalbumin, gelatin, and ossein), and smaller organics such as lecithin (1-stearoyl-2-oleoyl phosphatidylcholine, SOPC) and Aethonium (1,2-ethylene-bis(N-dimethyl carbodecyl oxymethyl) ammonium dichloride) with nanosilicas A-300 (S(BET)=232 and 297 m(2) g(-1)) and A-50 (S(BET)=52 m(2)g(-1)) was studied using dynamic light scattering, adsorption, and infrared (FTIR) spectroscopy methods. Time-dependent rearrangement of particle size distributions (PSDs) depicts appearance of both smaller and larger aggregates for silica/PEG(I-first adsorbate)/BSA(II-second adsorbate) and silica/PVP(I)/BSA(II) (i.e., BSA adsorbs onto PEG/silica or PVP/silica) than that for silica/organic compound I. However, in the cases of PVA(I)-BSA(II) and PVA(I)-SOPC(II) a similar effect is not observed because only increased aggregation occurs. The successive equilibrium adsorption of similar pairs shows a diminution of the adsorption of the second compound (gelatin, ovalbumin) with increasing amount of the first adsorbed polymer (PEG or PVP).

Weakly and strongly associated nonfreezable water bound in bones.

Water bound in bone of rat tail vertebrae was investigated by 1H NMR spectroscopy at 210-300 K and by the thermally stimulated depolarization current (TSDC) method at 190-265 K. The 1H NMR spectra of water clusters were calculated by the GIAO method with the B3LYP/6-31G(d,p) basis set, and the solvent effects were analyzed by the HF/SM5.45/6-31G(d) method. The 1H NMR spectra of water in bone tissue include two signals that can be assigned to typical water (chemical shift of proton resonance deltaH=4-5 ppm) and unusual water (deltaH=1.2-1.7 ppm). According to the quantum chemical calculations, the latter can be attributed to water molecules without the hydrogen bonds through the hydrogen atoms, e.g., interacting with hydrophobic environment. An increase in the amount of water in bone leads to an increase in the amount of typical water, which is characterized by higher associativity (i.e., a larger average number of hydrogen bonds per molecule) and fills larger pores, cavities and pockets in bone tissue.

Unusual properties of water at hydrophilic/hydrophobic interfaces.

The behaviour of water at mosaic hydrophilic/hydrophobic surfaces of different silicas and in biosystems (biomacromolecules, yeast cells, wheat seeds, bone and muscular tissues) was studied in different dispersion media over wide temperature range using 1H NMR spectroscopy with layer-by-layer freezing-out of bulk water (close to 273 K) and interfacial water (180 < T < 273 K), thermally stimulated depolarization current (TSDC) (90 < T < 270 K), infrared (IR) spectroscopy, and quantum chemical methods. Bulk water and water bound to hydrophilic/hydrophobic interfaces can be assigned to different structural types. There are (i) weakly associated interfacial water (1H NMR chemical shift delta(H) = 1.1-1.7 ppm) that can be assigned to high-density water (HDW) with collapsed structure (CS), representing individual molecules in hydrophobic pockets, small clusters and interstitial water with strongly distorted hydrogen bonds or without them, and (ii) strongly associated interfacial water (delta(H) = 4-5 ppm) with larger clusters, nano- and microdomains, and continuous interfacial layer with both HDW and low-density water (LDW). The molecular mobility of weakly associated bound water is higher (because hydrogen bonds are distorted and weakened and their number is smaller than that for strongly associated water) than that of strongly associated bound water (with strong hydrogen bonds but nevertheless weaker than that in ice Ih) that results in the difference in the temperature dependences of the 1H NMR spectra at T < 273 K. These different waters are also appear in changes in the IR and TSDC spectra.

Morphology and surface properties of fumed silicas.

Several series of fumed silicas and mixed fumed oxides produced and treated under different conditions were studied in gaseous and liquid media using nitrogen and water adsorption-desorption, mass spectrometry, FTIR, NMR, thermally stimulated depolarization current (TSDC), photon correlation spectroscopy (PCS), zeta potential, potentiometric titration, and Auger electron spectroscopy methods. Aggregation of primary particles and adsorption capacity (Vp) decrease and hysteresis loops of nitrogen adsorption-desorption isotherms becomes shorter with decreasing specific surface area (S(BET)). However, the shape of nitrogen adsorption-desorption isotherms can be assigned to the same type independent of S(BET) value. The main maximum of pore size distribution (gaps between primary nonporous particles in aggregates and agglomerates) shifts toward larger pore size and its intensity decreases with decreasing S(BET) value. The water adsorption increases with increasing S(BET) value; however, the opposite effect is observed for the content of surface hydroxyls (in mmol/m2). Associative desorption of water (2(SiOH)-->SiOSi+H2O) depends on both the morphology and synthesis conditions of fumed silica. The silica dissolution rate increases with increasing S(BET) and pH values. However, surface charge density and the modulus of zeta-potential increase with decreasing S(BET) value. The PCS, 1H NMR, and TSDC spectra demonstrate rearrangement of the fumed silica dispersion depending on the S(BET) value and the silica concentration (C(SiO2)) in the aqueous suspensions. A specific state of the dispersion is observed at the C(SiO2) values corresponding to the bulk density of the initial silica powder.

Structured water in partially dehydrated yeast cells and at partially hydrophobized fumed silica surface.

Nonfreezable water structured due to interaction with endocellular objects in yeast cells (endocellular water) or with partially hydrophobic fumed silica (interfacial water) was studied by means of (1)H NMR spectroscopy with layer-by-layer freezing-out of bulk water and quantum chemical methods applied to water clusters in the gas and liquid (chloroform and cyclohexene) phases and adsorbed on silylated silica. Variation in cell hydration as well as in amount of water adsorbed on modified fumed silica leads to changes in the ratio between contributions of two water states characterized by NMR chemical shifts at delta(H)=1.1-1.7 and 4-5 ppm. Lowering of hydration and temperature results in an enhancement of the first signal, and the opposite result is observed for the second signal. These effects may be explained by structured water distribution in the form of relatively large nanodroplets (delta(H)=4-5 ppm is close to that for bulk water) and small clusters of the 2D structure, in which the fraction of hydrogen atoms out of the hydrogen bonds (delta(H)=1.1-1.7 ppm) is larger than that in nanodroplets.

Study of interaction of proteins with fumed silica in aqueous suspensions by adsorption and photon correlation spectroscopy methods.

The interaction of fumed silica A-300 (S(BET) = 297 m2 g(-1)) with bovine serum albumin (prepared by different methods), ovalbumin, human hemoglobin, and gelatin as a function of pH, salinity, and concentrations of components in aqueous medium was studied by adsorption and photon correlation spectroscopy (PCS) methods. Comparison of equilibrium (incubation time t(i) approximately 1 h) adsorption of proteins on A-300, minute (t(i) approximately 1 min) flocculation rate, and the particle size distributions measured by the PCS method shows different rearrangement of particle swarms depending on pH, salinity, and concentration of proteins, especially at pH close to IEP of silica or proteins. The electrokinetic mobility of protein/silica swarms is greater than that of individual components at pH far from the IEP of proteins. Changes in the Gibbs free energy (DeltaG) on protein adsorption depend on pH (-DeltaG is minimal at pH 2, close to the IEP of silica, and maximal at pH between the IEP of protein and silica), concentration (-DeltaG is maximal at C(p) between 1 and 6 mg/ml), type of proteins, and their preparation technique.

Characteristics of modified Cab-O-Sil in aqueous media.

Fumed silica Cab-O-Sil HS-5 grafted with 3-aminopropyldimethylsilyl (APDMS), butyldimethylsilyl (BDMS), octadecyldimethylsilyl (ODDMS), and trimethylsilyl (TMS) groups of different concentrations were studied using photon correlation spectroscopy, electrophoresis, potentiometric titration, and nitrogen adsorption methods. Calculations of both electrophoretic mobility and zeta potential were performed taking into consideration the topological structure of "porous" aggregates of primary particles of fumed silica using two different approaches. Changes in surface charge density and the textural, aggregative, and electrophoretic characteristics of modified silicas depend on the type of grafted OSC, its chain length, polarity, and surface concentration. Particle swarms of initial and modified silicas in aqueous suspension are typically characterized by bimodal size distributions between 20 and 300 nm (aggregates) and 1-3 microm (agglomerates of aggregates). The difference between parameter values computed according to the Smoluchowski theory and improved approaches increases with increasing pH and is concordant for both mobility and zeta potential.