Salt effect on surface modification of silica by interpolyelectrolyte complexes

The effect of a low-molecular-mass salt on the properties of interpolyelectrolyte complexes formed as a result of interactions between poly(diallyldimethylammonium chloride) and copolymers of maleic acid with propylene or α-methylstyrene in their salt containing non-stoichiometric mixtures has been studied. Properties of such interpolyelectrolyte complexes were found to be determined by the chemical nature of the polyelectrolytes and by the salt concentration. The effect of salt on the surface modification of silica particles via their interactions with interpolyelectrolyte complexes has been examined. Two different ways of the surface modification of silica particles were used: (i) silica particles were contacted with previously prepared interpolyelectrolyte complexes and (ii) silica particles were contacted with cationic polyelectrolyte at first and then anionic polyelectrolyte was added. The efficiency of the surface modification was shown to be also dependent on the salt concentration and the chemical nature of polyelectrolytes. Turbidimetry, quasi-elastic light scattering, laser microelectrophoresis, and polyelectrolyte titration were used to characterize studied systems.     

Effect of Variant Counterions on Stability and Particle Size of Silica Sol

The effects of variant counterions with ionic strength of 0.05, 0.10, 0.20 and 0.25 mol·kg^-1 on the stability and particle size of silica sols have been studied using the traditional methods of Ubbelohde viscosity measurement, TEM and titration respectively, finding that the stability and particle size of the silica sols are all concerned with the acidic, positively electric properties and the sizes of the counterions, as well as the attraction between the counterions and surface silicon hydroxyl groups of the silica sols. The small positively charged counterions lead to the decrease in particle sizes, making the silica sol the most stable. But the larger weakly acidic counterions can restrict the particle sizes of the silica sols and easily make the sols coagulate. It was also found that there existed a linear relationship between log r and log η, which has not ever been reported. The effect of temperature on the stability and particle sizes was also discussed.     

Stabilization of <Emphasis Type="Italic">n</Emphasis>-aminopropyl silica gel against hydrolysis by blocking silanol groups with TiO<Subscript>2</Subscript> or ZrO<Subscript>2</Subscript>

Silanol groups of n-aminopropyl silica gel (APSG) were blocked with TiO₂ or ZrO₂ to produce Ti-APSG and Zr-APSG, respectively. The silica materials were characterized by infrared, Raman spectra, thermogravimetric, elemental analyses, magic angle spinning ¹³C-nuclear magnetic resonance, specific surface area measurements, pH-metric titration and inductively coupled plasma—optical emission spectrometry—monitored silica hydrolysis. The stability of APSG against hydrolysis was found to be mainly affected by the specific surface area and the basicity of the n-aminopropyl groups which acquire additional strength from their intramolecular interaction with the silanol groups. The hydrolysis of silica in Ti-APSG and Zr-APSG remarkably decreased in the range of pH 1.0–9.1 due to the interruption of that intramolecular interaction. The hydrolyzed silica of Ti-APSG and Zr-APSG was decreased to 22.7 and 29.9%, respectively, of that of APSG at pH 4.5. Capacity and stability of Ti-APSG and Zr-APSG were improved in comparison with APSG upon application in the extraction of Cu²⁺ for 20 cycles of extraction and regeneration.     

Adsorption of poly(vinyl formamide-co-vinyl amine) onto silica particle surfaces and stability of the formed hybrid materials

In order to produce silica/polyelectrolyte hybrid materials the adsorption of the polyelectrolyte poly(vinyl formamide-co-vinyl amine), P(VFA-co-VAm) was investigated. The adsorption of the P(VFA-co-VAm) from an aqueous solution onto silica surface is strongly influenced by the pH value and ionic strength of the aqueous solution, as well as the concentration of polyelectrolyte. The adsorption of the positively charged P(VFA-co-VAm) molecules on the negatively charged silica particles offers a way to control the surface charge properties of the formed hybrid material. Changes in surface charges during the polyelectrolyte adsorption were studied by potentiometric titration and electrokinetic measurements. X-ray photoelectron spectroscopy (XPS) was employed to obtain information about the amount of the adsorbed polyelectrolyte and its chemical structure. The stability of the adsorbed P(VFA-co-VAm) was investigated by extraction experiments and streaming potential measurements. It was shown, that polyelectrolyte layer is instable in an acidic environment. At a low pH value a high number of amino groups are protonated that increases the solubility of the polyelectrolyte chains. The solvatation process is able to overcompensate the attractive electrostatic forces fixing the polyelectrolyte molecules on the substrate material surface. Hence, the polyelectrolyte layer partially undergoes dissolving process.     

MgO－B2O3－MgCl2－H2O体系与盐酸滴定反应的研究

ＭｇＯ－Ｂ２Ｏ３－ＭｇＣｌ２－Ｈ２Ｏ是含硼盐湖日晒浓缩盐卤的典型体系，它与盐酸反应生成硼酸，是从天然浓缩盐卤中制取硼酸的工艺基础，以量热滴定法和ＰＨ滴定法研究该反应，结果表明，析出硼酸的反应分两步进行；合成盐卤中硼酸盐可用ＭｇＢ２ｎＯ３Ｎ＋１（ｎ＝１，２，３）综合统计形式来表示；天然浓缩盐卤中硼酸盐可以用四硼酸镁的统计形式进行表示。     

Controlled synthesis of stable poly(vinyl formamide-co-vinyl amine)/silica hybrid particles by interfacial post-cross-linking reactions

 The chemical synthesis and the physicochemical properties of stable poly(vinyl formamide-co-vinyl amine)/silica hybrid particles are presented. Copolymers of poly(vinyl formamide) (PVFA) and poly(vinyl amine) (PVAm) and their protonated forms were adsorbed onto silica from aqueous solutions. The influences of the pH strength and the ion concentration of the aqueous solution as well as the copolymer composition (degree of hydrolyzation of PVFA), and the molecular mass on the adsorption process were investigated by electrokinetic measurements, potentiometric titration, and quantitative elemental analyses. Silica surface-charge neutralization is achieved at a pH strength above 10 for highly hydrolyzed (95%) PVFA polymers. Decreasing the amino content in the PVAm chain shifts successively both the point of zero charge and the isoelectric point to lower pH values. PVFA-co-PVAm layers onto silica are adsorbed weakly. To fix these layers irreversibly, cross-linking reactions with (4,4′-diisocyanate)diphenyl methane were carried out on the surface of solid PVFA-co-PVAm/silica hybrid particles suspended in acetone. The cross-linking reaction, which is connected with the conversion of amino groups, is also a tool to control the surface charge of the PVFA-co-PVAm/silica hybrids. X-ray photoelectron spectroscopy and solid-state ¹³C cross-polarization magic-angle spinning NMR spectroscopy were used to obtain information on the number of and the structure of the functionalized polyelectrolyte layers on silica. The success of cross-linking was also shown by the results of these spectroscopic methods. Received: 28 June 1999 /Accepted: 27 August 1999     

Protolytic equilibria on the surface of carboxyl-containing silica

Potentiometric titration has been used to study the protolytic equilibria on the surface of carboxyl-containing silica (CS) prepared by the reaction of silica (Silokhrom S-80, S_sp = 80 m²/g) with Cl₃SiCH₂CH₂COOCH₃, followed by hydrolysis with 30% sulfuric acid. The titration curve of the vacuum-dried sample is irreversible. The titration curve of its Na⁺ form with hydrochloric acid proceeds lower than the titration curve of its H⁺ form and coincides with the titration curve of the air-dried sample (the last curve is reversible). The titration curve of CS coincides with the titration curve of butyric acid at pH < 6. At pH > 6 the titration curve of CS passes below the titration curve of butyric acid; this is due to the participation of silanol groups on the silica surface in the protolytic equilibria. The pK_a of the grafted CS groups is equal to 4.80 which is close to the pK_a value of butyric acid (4.78). A method has been proposed for the determination of the amount of weak acid groups grafted to the silica. It has been shown that in the titration of CS the equilibrium is established much faster than in the case of the unmodified silica.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 2, pp. 243–247, March–April, 1986.     

An NMR study of the species produced by the reactions of dialkyl magnesium and HCl with calcined silica and the polymerisation performance of Ziegler-Natta catalysts produced from this support material

The effect of calcinations on the silica surface groups and thereby on the activity of Ziegler-Natta catalysts in ethylene homopolymerisation has been studied. Silica was calcined at different temperatures and treated with MgR₂ and HCl. Silica surface groups were identified by using ¹H MAS NMR and ¹³C and ²⁹Si CP MAS NMR techniques. Magnesium, titanium and chlorine were measured by elemental analysis. Ziegler-Natta catalysts were prepared from these supports and subsequently used in ethylene homopolymerisation. Maximum activity was obtained with the catalyst based on 590 °C calcined silica. The results indicate that MgR₂ reacts with siloxane-groups (Si-O-Si) in the 300 °C calcined silica, leaving the hydrogen-bonded hydroxyl-groups unreacted. Low activity Si-O-Ti(Cl)₂-O-Si species are formed after reacting with TiCl₄. The higher activity in the catalyst based on 590 °C calcined silica can be explained by the formation of -Si(R)-O-Si-O-TiCl₃ groups, originating from the siloxane bridges which cannot form in 300 °C calcined silica. Other explanations for the higher activity are a higher Mg/Ti ratio or small amounts of crystal water formed in the 590 °C calcined silica.     

Adsorption of Cd(II) by Sol-Gel Silica Doped with N-(dipropylcarbamothioyl)thiophene-2-carboxamide

Sol-gel silica was doped with N,N-(dipropylcarbamothioyl) thiophene-2-carboxamide to investigate the sorption of cadmium (Cd) ions from aqueous media. In doped sol-gel silica, the large reagent molecules entrap into pores, whereas, small metal ions diffuse into pores where they make complex with doped reagent. This complexation can be accomplished by either ion exchange or chelation. Doped sol-gel sorbent was applied for removal of Cd(II) from aqueous solution in our study. Adsorption kinetics, adsorption isotherm, equilibration time, effect of initial concentration of adsorbate, and pH effect on the metal removal were studied to optimize the conditions. The prepared adsorbent shows rapid equilibrium and high stability toward high temperature and applied medium. In addition, desorption of metal ions was carried out by 1 M HCl and, thereafter, sol-gel silica adsorbent was regenerated and reused periodically.     

Supramolecular Recognition of Amino Acids by Twisted Cucurbit[14]uril

Binding interactions between twisted cucurbit[14]uril (tQ[14]) and twenty standard amino acids (AAs) have been investigated by NMR spectroscopy and isothermal titration calorimetry (ITC) in aqueous HCl solutions and in DMSO. The results showed that tQ[14] displays clear binding affinity for AAs with a positively charged side chain or containing an aromatic ring, but weaker binding affinity for AAs with hydrophobic or polar side chains, with the binding mode depending on the type of side chain present in the AAs.     

Hydrophilic Sites on Silica Surface Modified in Gaseous and Liquid Phases

The methods of chromatography, adsorption, and potentiometic titration were used to determine the amount and energetics of the residual hydrophilic sites on the wide-porous silica surfaces modified in gaseous and liquid phases. The concentration of the residual hydrophilic sites on the silica surfaces modified by both methods was shown virtually to be the same. However, the activity of the hydrophilic sites on the sample modified in gaseous phase was significantly higher than that on the sample modified by liquid-phase method. Based on the comparison of the calculated isosteric heats of adsorption of water vapors on the studied modified sorbents with calorimetric heats, which are characteristic for the interaction of water molecules with vicinal and single hydroxyl groups of silica gel, the nature of the residual hydrophilic sites on the silica surfaces modified by these two methods was discussed.     

Adsorption of potential-determining ions on porous glasses of different compositions

The adsorption characteristics are studied for nano- and ultraporous glasses (PGs) produced from sodium borosilicate glasses and a glass containing small amounts of fluoride ions and phosphorus oxide by acid (HCl) leaching and additional alkaline (KOH) and thermal treatment. The surface charges σ₀ of PGs are determined by continuous potentiometric titration in 10⁻³−1 M NaCl, KCl, and (C₂H₅)₄NCl solutions. Only negative surface charges of PGs are observed for all investigated systems. The |σ₀| value is predetermined by the following factors: the composition of PG, the pore radius in the nanometer region (r ≤ 13 nm), the specificity of counterions, the content of secondary silica in the pore space, and the temperature of the additional thermal treatment of the membranes. The introduction of fluoride ions and phosphorus oxide into sodium borosilicate glass, an increase in the pore sizes and the amount of the secondary silica in PGs, and a rise in the specificity of counterions enhance the |σ₀| values, which decrease with a rise in the temperature of the thermal treatment due to the surface dehydration and dehydroxylation. For ultraporous glasses (r > 13 nm), the surface charge is almost independent of the pore radius.     

Graft polymerization of methyl methacrylate from silica initiated by peroxide groups introduced onto the surface

The surface grafting onto ultrafine silica by the radical polymerization of methyl methacrylate (MMA) initiated by peroxide groups introduced onto the surface was investigated. The introduction of peroxide groups onto the silica surface was achieved by the reaction of hydrogen peroxide with chlorosilyl groups, which were introduced by the treatment of silica with thionyl chloride. The content of diisopropylbenzene peroxide and tert-butyl peroxide groups introduced onto the silica according to the above method was determined to be 0.11 and 0.08 mmol/g, respectively. It was found that the polymerization of MMA is initiated by silica having these peroxide groups. In the polymerization, polyMMA was grafted onto silica surface: the percentage of grafting reached about 70%. Therefore, it was concluded that the polymerization of MMA is initiated by surface radicals formed by the decomposition of peroxide groups on silica and polyMMA is grafted through the propagation from the surface. During the polymerization, ungrafted polyMMA was also formed because of the formation of initiator fragments by the decomposition of peroxide groups: the grafting efficiency of the graft polymerization was 30–40%. PolyMMA-grafted silica produced a stable colloidal dispersion in organic solvents for polyMMA. © 1992 John Wiley & Sons, Inc.     

The formation mechanism of cobalt silicide on silica from Co(SiCl3)(CO)4 by in situ Fourier transform infrared spectroscopy

Silica supported CoSi particles were synthesized by metal organic chemical vapor deposition of the Co(SiCl(3))(CO)(4) precursor carried in hydrogen at atmospheric pressure and moderate temperature in a fluidized bed reactor. In contrast, CoCl(2) supported on silica was formed by using argon as the carrier gas. The samples were characterized by X-ray diffraction, transmission electron microscopy, ultraviolet-visible spectroscopy, and thermogravimetric/differential thermogravimetric analysis. The precursor Co(SiCl(3))(CO)(4) reacted with the hydroxyl groups of amorphous silica via loss of HCl and introduced cobalt species onto the surface. The decomposition mechanism of the supported precursor on silica was investigated by in situ Fourier transform infrared spectroscopy from room temperature to 300 °C in a hydrogen or argon atmosphere. The results showed that CO and HCl elimination occurred in a hydrogen atmosphere, while only CO elimination occurred in Ar. All of the results showed that it was possible to prepare supported CoSi at lower temperatures via changing the carrier gas.     

Chemical tailoring of porous silica xerogels: local structure by vibrational spectroscopy

Monolithic porous silica xerogels were synthesized by the sol-gel process, and their local structure was analysed by vibrational spectroscopy. The silica alcogels were prepared by a two-step hydrolytic polycondensation of tetraethoxysilane (TEOS) in isopropanol, with a water/TEOS molar ratio of 4. The hydrolysis step was catalysed by hydrochloric acid (HCl), with different HCl/TEOS molar ratios (ranging from 0.0005 to 0.009), and the condensation step was catalysed by ammonia (NH(3)), with different NH(3)/HCl molar ratios (ranging from 0.7 to 1.7). After appropriate ageing, the alcogels were washed with isopropanol and subcritically dried at atmospheric pressure. The diffuse reflectance infrared Fourier transform (DRIFT) spectra were analysed in terms of the main siloxane rings that form the silica particles, taking into account the splitting of the nu(as)Sibond;Obond;Si mode into pairs of longitudinal and transverse optic components, by long-range Coulomb interactions. It was proven that the proportion of residual silanol groups (which correlates with hydrophilicity), and the fraction of siloxane 6-rings (which correlates with porosity) may be tailored by adequate catalytic conditions, mostly by the hydrolysis pH. This was explained in terms of the reactions' mechanisms taking place in the two-step sol-gel process followed.     

Acid–Base Properties of Macroporous Weak Base Anionite Based on Aminated Acrylonitrile/Divinylbenzene Copolymer

Potentiometric titration of weak base anionite (the degree of crosslinking was 12–16%) was performed within the pH range of 2–12 and NaCl concentration range of 0.1–1.0 mol/L. The maximum ionexchange ability against HCl does not depend on the solution ionic strength and is 6.50 ± 0.12 mmol/g of dry solid matter. It was shown that the process of acid–base equilibrium can be adequately described by the Gregor equation within the studied stock electrolyte concentration and pH ranges. Two type of groups were discovered in anionite. The ionization constants of these groups differ by three orders of magnitude. The existence of amino groups of different nature was proved by the data obtained by functional analysis; it was estimated that the acidity of these groups decreases as NaCl concentration increases.     

Effects of ferrocenyl group on refractive index of colloidal crystal system formed by polymer-grafted silica in organic solvent

Colloidal crystallization of copolymer-grafted silica containing ferrocenyl groups in organic solvents and effects of ferrocenyl groups on effective refractive index of colloidal crystal systems were investigated. Poly(ferrocenyl metharylate (FeMA)-co-methyl methacrylate (MMA)-grafted silica gave colloidal crystallization in dimethylformamide and acetonitrile. The colloidal crystals exhibited characteristic coloration due to cooperative effects of specific absorption at 400–500 nm by ferrocenyl group and transmission of 700–800-nm light through the crystals. It was observed that effective refractive index of colloidal crystals systems of poly(FeMA-co-MMA)-grafted silica was higher than that of poly(MMA)-grafted silica. Normalized effective refractive index of the system linearly increased with mole fraction of FeMA in grafted copolymer. However, poly(FeMA-block-MMA) did not bring effective increase of the index because of bias formation of ferrocenyl group on silica.     

Features of the Sorptive Extraction of Osmium in Different Oxidation States with Silica Gels Chemically Modified with Mercapto and Disulfide Groups

The sorptive extraction of osmium(VIII, VI, IV) from HCl solutions with silica gels chemically modified with mercapto groups (MPS) and disulfide groups (DPDSS) was studied. The recovery of osmium(VIII) from 0.5–4 M HCl is 99 and 25% with the sorption equilibration time 5 and 20 min for MPS and DPDSS, respectively. The equilibration time for the extraction of Os(VI) with MPS is no longer than 1 min. The recovery from 0.1–4 M HCl is up to 99.9%. The recovery of osmium(VI) with DPDSS decreases from 96 and 80% when going from 0.5 M to 4 M HCl. The quantitative extraction of osmium(IV) is attained at 95°C in the presence of tin(II) chloride and the equilibration time 60 min. Without tin(II) chloride, osmium(IV) is not extracted with these sorbents. The difference in the sorption ability of chemically modified silica gels with respect to osmium in different oxidation states can be used for the extraction of osmium(VI) and osmium(IV) and their separate determination directly in the MPS phase with the use of diffuse reflectance spectrometry.     

Fraction of H-bonded segments of N-ethylpyrrolidone,oligomeric and polymeric vinylpyrrolidone adsorbed from CHCl3 on silica measured by IR spectrometry

The adsorption of N-ethylpyrrolidone (NEP), oligomeric and polymeric vinylpyrrolidone (OVP, PVP) on silica (Aerosil 200) from CHCl₃ solution is investigated by IR spectrometry. The influence of the annealing temperature of the silica on the adsorbed amount and on the fraction of adhered segments was studied. The dependences of the amount adsorbed on solution concentration result for NEP in a Langmuir isotherm for OVP and PVP in high affinity isotherms. The fraction of adhered H-bridged carbonyl groups determined by compensation procedures, the fraction of surface SiOH groups occupied and the multiple interaction quotientQ show different dependences on the amount adsorbed for the measured adsorptives, indicating different interactions of the monomeric segments with the surface groups. This behaviour is explained by comparing the amount adsorbed in saturation with monolayer capacities, surface concentration of SiOH groups and frequency shifts. A splitting of the band of the bound carbonyl groups in a double peak was observed with OVP and PVP, referring to an additional interaction of polymer segments neighboured to specifically bound segments.Herrn Professor Dr. Robert Kerber zum 60. Geburtstag gewidmet.     

Selective preconcentration of uranyl ion by silica gel phases modified with chelating compounds as inorganic polymeric ion exchangers.

Four chemically modified chelating silica gel phases (I - IV) with ion exchange groups were tested for their potential capability to selectively bind, extract and preconcentrate uranyl ions (UO(2)(2+)) from different aqueous solutions as well as ore samples. Factors affecting such determination processes were studied and optimized. These included the pH of the contact solution, the mass of the silica gel phase extractant, the stirring time during the application of a static technique and the eluent concentration for desorption of the surface-bound uranyl ion and interfering anions and cations. All these factors were evaluated on the basis of determinations of the distribution coefficient value (K(d)) and the percent recovery (R%). Percent recovery values of 91% for silica phase (II) and 93% for silica phase (IV) were identified in the optimum conditions. The proposed preconcentration method was further applied to uranium ore samples as well as granite samples. The determined percentage and ppm values are in good agreement with the standard assigned ones. The structure of the synthesized silica gel phases (I - IV) and their uranyl bound complexes were identified and characterized by means of infrared analysis, thermal analysis (TGA) and potentiometric titration.