Aluminum-27 NMR Investigations of Aqueous and Methanolic Aluminosilicate Solutions

Aluminum-27 NMR spectroscopy was used to characterize aqueous and methanolic alkaline solutions of tetramethylammonium (TMA) aluminosilicates. Aluminosilicate solutions have been prepared with different concentrations of silicon [0.577–1.24% (w/w)], aluminum [0.0022–0.239% (w/w)], methanol [0.0–0.70% (w/w)] and H₂O [0.23–90% (w/w)]. All solutions contain the same ratio of Si/TMA = 1 and Si/Al molar ratios between 0.5 and 25.²⁷Al NMR spectra of TMA aluminosilicate solutions are characterized by a variety of aluminosilicate species such as q¹(Al1OSi), q²(Al2OSi), q³(Al3OSi) and q⁴(Al4OSi). Aluminum-27 NMR spectra of TMA aluminosilicate solutions indicate that considerable changes occurred by changing the Si/Al ratio. The distribution of aluminosilicate species was affected by the presence of the methanol and the method of mixing the silicate and aluminosilicate solutions. A methanolic aluminosilicate solution needs about twice the time required for an aqueous aluminosilicate solution to reach a steady state, i.e., the latter takes 36 h to reach steady state. Results with the same concentration of silicon and aluminum show that the formation and distribution of aluminosilicate species are strongly dependent on the solvent comprising the silicate and aluminate solutions.     

Novel Method of Producing Polymer Gels in Aqueous Solution Using UV Irradiation

Summary: We developed a novel method of producing polymer gels in aqueous solution using UV irradiation. Persulfates were effective photosensitive initiators of polymerization and/or gelation of acryloyl‐type monomers/polymers. The gelation was confirmed by an abrupt increase in light scattering intensity, 〈I(q)〉_T, at the gelation point. The gelation method entails significant advantages: it does not need any cross‐linkers, temperature control (heating), and additives except the persulfate.

The UV irradiation time dependence of light scattering intensity, 〈I(q)〉_T, for pre‐gel solutions containing N‐isopropylacrylamide (NIPAm) and/or ammonium persulfate (APS).     

Phase separation in mixtures of poly(ethylene glycol monomethylether) and poly(propylene glycol) oligomers

Time-resolved light scattering was employed to investigate kinetics of phase separation in mixtures of poly (ethylene glycol monomethylether) (PEGE)/poly (propylene glycol) (PPG) oligomers. Phase diagrams for PEGE/PPG of varying molecular weights were established by means of cold point measurements. The oligomer mixtures reveal an upper critical solution temperature (UCST). Several temperature quench experiments were carried out with a 60/40 PEGE/PPG blend by rapidly quenching from a single phase (69°C) to two-phase temperatures (66–61°C) at 1°C intervals. As is typical for oligomer mixtures, the early stage of spinodal decomposition (SD) was not detected. The kinetics of phase decomposition was found to be dominated by the late stage of SD. Time-evolution of scattering intensity was analyzed in accordance with nonlinear and dynamical scaling theories. The time dependence of the peak intensity I_m and the corresponding peak wavenumber q_m was found to follow the power-law {I_m(t)? t^α, q_m(t)? t^-β} with the values of α = 3 ± 0.3 and β = 1 ± 0.2, which are very close to the values predicted by Siggia. This process has been attributed to a coarsening mechanism driven by surface tension. In the temporal scaling analysis, the structure function reveals university with time, suggesting self-similarity. Phase separation dynamics in 60/40 PEGE/PPG resembles the behavior predicted for off-critical mixtures.     

Dynamic light scattering of semidilute hydrophobically modified alkali‐soluble emulsion solutions with different lengths of poly(ethylene oxide) spacer chain

Semidilute solutions of hydrophobically modified alkali‐soluble emulsion (HASE) were examined by dynamic light scattering and rheological techniques. For the model polymer without associative macromonomer, two q² dependent diffusional modes were detected in the decay time distributions. With increasing hydrophobicity of the associative macromonomer, the narrow fast peak was substituted by a shallow broad peak and only one q² dependent slow mode could be accurately detected, which indicated that the heterogeneity of these associated clusters increases with increasing carbon number. The bulk steady‐shear viscosity exhibits similar results to the diffusion coefficients of the aggregate observed from light scattering measurements. The length of poly(ethylene oxide) (PEO) spacer chain alters the solution properties as well as the associative cluster structure. With increasing length of PEO spacer chain, intramolecular association was substituted by intermolecular association. For EO segment larger than 32 units, intramolecular association dominates, where the formation of HASE aggregates is controlled by the balance of electrostatic repulsion and hydrophobic attraction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3288–3298, 2005     

Hydrolysis of methyltin(IV) trichloride in aqueous NaCl and NaNO3 solutions at different ionic strengths and temperatures

The hydrolysis of methyltin(IV) trichloride (CH₃SnCl₃) has been studied in aqueous NaCl and NaNO₃ solutions (0 < I/mol dm⁻³ ≤ 1), at different temperatures (15 ≤ T/°C ≤ 45) by­potentiometric measurements (H⁺‐glass electrode). By considering the generic hydrolytic <?tw=97.2%>reaction pCH₃Sn³⁺ + qH₂O = (CH₃Sn)_p(OH)_q^3p−q<?tw>­+ qH⁺ (logβ_pq), we have the formation of five species and logβ₁₂ = −3.36, logβ₁₃ = −8.99, logβ₁₄ = −20.27 and logβ₂₅ = −7.61. The first hydrolysis step is measurable only at very low pH values and was not determined: a rough estimate of the hydrolysis constant is logβ₁₁ = −1.5 (± 0.5). The dependence on ionic strength of logβ_pq is quite different in NaNO₃ and NaCl solutions, and the formation at low pH values of the species CH₃Sn(OH)Cl⁺ has been found with logβ = −1.40. Hydrolysis constants strongly depend on temperature and from the relationships logβ_pq = f(T), ΔH ° values have been calculated. Speciation problems of CH₃Sn³⁺ in aqueous solution are discussed. Copyright © 1999 John Wiley & Sons, Ltd.     

Homogeneous methylation of wood pulp cellulose dissolved in LiOH/urea/H2O

Spruce sulphite cellulose (number average degree of polymerization 620) dissolved in an aqueous solution of 8% (w/w) LiOH*H₂O and 12% (w/w) urea was methylated with dimethyl sulphate (DMS). By varying the reaction temperature between 22 and 50 °C, the molar ratio between 9 and 15 mol DMS per mol anhydroglucose unit, and the reaction time from 4 to 24 h, methyl cellulose (MC) with degree of substitution (DS) values in the range of 1.07 and 1.59 was prepared. The chemical structure of MC was analysed by FTIR and ¹H NMR spectroscopy. The turbidity (given in nephelometric turbidity units, NTU) of the aqueous solution of MC reached an optimum of 10 NTU for a product obtained with 12 mol DMS/mol AGU at 50 °C. GPC measurements revealed polymer degradation to a certain extent. The intrinsic viscosity and the Huggins constant k of the MC samples increased with increasing DS value. The MC samples possess k values higher than 0.8, indicating association of the polymer chain. The zero-shear viscosity decreased with increase of both temperature and the amount of methylation agent due to the depolymerization. During the heating/cooling cycle (20-90 °C) of the aqueous solutions of MC, it was observed that samples synthesized at 22 °C with DS values lower than 1.3 did not undergo phase separation in aqueous solution. Phase separation hysteresis with a precipitation temperature up to 80 °C was obtained for aqueous solutions of MC with DS values between 1.07 and 1.66 synthesized at higher temperatures. The functionalization pattern determined by GLC of the corresponding partially methylated glucitol acetates is close to randomness and comparable with those of commercial MC samples.     

Rheological and structural properties of aqueous solutions of a hydrophobically modified polyelectrolyte and its unmodified analogue

Rheological methods and small angle neutron scattering (SANS) were used in the characterization of dilute and semidilute aqueous solutions, both with and without added salt, of anionic poly(vinyl alcohol) (PVA⁻) and its hydrophobically modified analogue (HM-PVA⁻). The rheological measurements showed that the concentration induced viscosification effect and elastic responses are considerably stronger for solutions of HM-PVA⁻ than in solutions of the unmodified polyelectrolyte. Over the considered polymer concentration domain, the solutions of PVA⁻ exhibit virtually Newtonian behavior, whereas strong shear thinning effects are observed in the HM-PVA⁻ solutions. The SANS results for HM-PVA⁻ solutions reveal a pronounced peak in the plot of scattering intensity versus scattering wavevector q at intermediate q values and the position of the maximum scales with polymer concentration as q_max∼c^0.28±0.02. This peak is suppressed in solutions of the unmodified polyelectrolyte and merely a shoulder in the scattering curve appears. Additionally, an “upturn” in the scattered intensity is observed at small q values and the magnitude of this effect depends on polymer concentration, hydrophobicity and salt addition. At large q values, the SANS results from HM-PVA⁻ solutions suggest morphological changes, from rod-like chains to a network of semiflexible chains, as the polyelectrolyte concentration increases.     

Spinodal decomposition and phase separation kinetics in nanoclay–biopolymer solutions

Intensity of light, I(q,t), scattered from homogeneous aqueous solutions, of nanoclay (Laponite) and protein (gelatin‐A), was studied to monitor the temporal and spatial evolution of the solution into a phase‐separated nanoclay–protein‐rich dense phase, when the sample temperature was quenched below spinodal temperature, T_s (=311 ± 3 K). The zeta potential data revealed that the dense phase comprised charge‐neutralized intermolecular complexes of nanoclay and protein chains of low surface charge. The early stage, t < 500 s, of phase separation could be described adequately through Cahn‐Hilliard theory of spinodal decomposition where the intensity grows exponentially, I(q, t) = I₀ exp.(2R(q)t). The wave vector, q dependence of the growth parameter, R(q) exhibited a maxima independent of time. Corresponding correlation length, 1/q_c = ξ_c was found to be ≈75 ± 5 nm independent of quench depth. In the intermediate regime, anomalous growth described by I(q, t) ～ t^α with α = 0.1 ± 0.02 independent of q was observed. Rheological studies established that there was a propensity of network structures inside the dense phase. Isochronal temperature sweep studies of the dense phase determined the melting temperature, T_m = 312 ± 4 K, which was comparable with the spinodal temperature. The stress‐diffusion coupling prevailing in the dense phase when analyzed in the Doi‐Onuki model yielded a viscoelastic correlation length, ξ_v determined from low‐frequency storage modulus, G ′₀ ≈ k_B T/ξ, which was ξ_v ≈ 35 ± 3 nm indicating 2ξ_v ≈ ξ_c. It is concluded that the early stage of phase separation in this system was sufficiently described by linear Cahn‐Hilliard theory, but the same was not true in the intermediate stage. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 555–565, 2010     

Influence of TMAO as co-solvent on the gelation of silica-PNIPAm core-shell nanogels at intermediate volume fractions

We study the structure and dynamics of poly(N-isopropylacrylamide) (PNIPAm) core-shell nanogels dispersed in aqueous trimethylamine N-oxide (TMAO) solutions by means of small-angle X-ray scattering and X-ray photon correlation spectroscopy (XPCS). Upon increasing the temperature above the lower critical solution temperature of PNIPAm at 33 °C, a colloidal gel is formed as identified by an increase of I(q) at small q as well as a slowing down of sample dynamics by various orders of magnitude. With increasing TMAO concentration the gelation transition shifts linearly to lower temperatures. Above a TMAO concentration of approximately 0.40 mol/L corresponding to a 1 : 1 ratio of TMAO and NIPAm groups, collapsed PNIPAm states are found for all temperatures without any gelation transition. This suggests that reduction of PNIPAm-water hydrogen bonds due to the presence of TMAO results in a stabilisation of the collapsed PNIPAm state and suppresses gelation of the nanogel.     

Evidence for hydrophobic attraction between latex particles in aqueous systems as investigated by turbidimetry

We report the evidence for attractive interaction of latex particles which are covered by poly(ethylene oxide) chains. These particles are suspended in aqueous solutions of ammonium sulfate. The interaction is probed by measurements of the turbidity of the suspensions up to 70 g/l. Turbidity is insensitive to multiple scattering and allows the static structure factor, S(q) [q=(4πn ₀/λ₀)sin(θ/2), where θ is the scattering angle, n₀ is the refractive index of the medium and λ₀ is the wavelength in vacuo], to be determined at small q values. The analysis of S(q) at small q values yields information about possible attraction of the particles. The analysis of the turbidity data furthermore shows that no aggregation took place in these systems. A weak but long-range attractive interaction was found at ammonium sulfate concentrations of 0.01 and 0.1 M. The relation of this attractive force to hydrophobic forces is discussed. Received: 9 March 2000/Accepted: 28 June 2000     

Characteristics of sorption of uncomplexed and complexed Pb(II) from aqueous solutions onto peat

Batch experiments aimed at the sorption of Pb(II) onto peat were performed from an aqueous solution in both the absence and presence of common complexing agents (acetate or citrate). The influence of the initial pH of the solution, metal ion concentration and contact time on the sorption efficiency of Pb(II) was examined at ambient temperature (18 ± 0.5) °C for each experiment. The results showed that the presence of acetate improved the efficiency of the sorption process, while the presence of citrate in the aqueous solution decreased the efficiency of the Pb(II) sorption onto peat. The equilibrium data fitted well with the Langmuir isotherm model and confirmed the monolayer sorption of uncomplexed and complexed Pb(II) species onto peat. The values of maximum sorption capacities (q _max) were 135.13 mg g⁻¹ for Pb(II) complexed with acetate, q > 79.36 mg g⁻¹ for uncomplexed Pb, q > 38.46 mg g⁻¹ for Pb(II) complexed with citrate. The kinetics of Pb(II) sorption onto peat, in both the absence and presence of complexing agents, indicated a pseudosecond order mechanism. Analysis of IR spectra showed that carboxylic and hydroxyl groups had an important role in the binding process of Pb(II) species onto peat.     

Reentrant behavior of poly(vinyl alcohol)–borax semidilute aqueous solutions

 The reentrant behavior of Poly(vinyl alcohol) (PVA)–borax aqueous semidilute solutions with a PVA concentration of 20 g/l and borax concentrations varies from 0.0 to 0.20 M was investigated using dynamic light scattering (DLS) and dynamic viscoelastic measurements. Two (fast and slow modes) and three (fast, middle, and slow) relaxation modes of PVA semidilute aqueous solutions without and with the presence of borax, respectively, were observed from DLS measurements. The fast and middle relaxation modes were q ²-dependent (q is the scattering vector) characteristic of diffusive behavior; however, the slow modes were q ³-dependent, characteristic of intraparticle dynamics. The experimental results showed that the slow relaxation mode dominates the DLS relaxation. The DLS slow mode relaxation time, τ_s, and the viscoelastic modulus G′(ω) and G′′(ω) data had a similar trend and demonstrated reentrant behavior as the borax concentration was increased from 0.0 to 0.20 M, i.e. τ_s, G′(ω), and G′′(ω) fluctuated with increasing borax concentration. The excluded-volume effect of polymers, charge repulsion among borate ions bound on PVA molecules, and intermolecular cross-linking didiol–borate complexation caused an expansion of the polymer chain; however, the screening effect of free Na⁺ ions on the negative charge of the borate ions bound on PVA and intramolecular cross-linking didiol–borate complexation led to a shrinkage of the polymer chain. The reentrant behavior was the consequence of the balance between expansion and shrinkage of the PVA–borate complex. Received: 26 March 1999/Accepted in revised form: 3 September 1999     

Quasielastic light scattering study of chemically crosslinked gelatin solutions and gels

Quasielastic light scattering measurements are reported for experiments performed on mixtures of gelatin and glutaraldehyde (GA) in the aqueous phase, where the gelatin concentration was fixed at 5 (w/v) and the GA concentration was varied from 1×10⁻⁵ to 1×10⁻³ (w/v). The dynamic structure factor, S(q,t), was deduced from the measured intensity autocorrelation function, g ₂(τ), with appropriate allowance for heterodyning detection in the gel phase. The S(q,t) data could be fitted to S(q,t)=Aexp(−D _f q ² t)+Bexp(−t/τ_c)^β, both in the sol (50 and 60 ^∘C) and gel states (25 and 40 ^∘C). The fast-mode diffusion coefficient, D _f showed almost negligible dependence on the concentration of the crosslinker GA; however, the resultant mesh size, ξ, of the crosslinked network exhibited strong temperature dependence, ξ∼(0.5−χ)^1/5exp(−A/RT) implying shrinkage of the network as the gel phase was approached. The slow-mode relaxation was characterized by the stretched exponential factor exp(−t/τ_c)^β. β was found to be independent of GA concentration but strongly dependent on the temperature as β=β₀+β₁ T+β₂ T ². The slow-mode relaxation time, τ_c, exhibited a maximum GA concentration dependence in the gel phase and at a given temperature we found τ_c(c)=τ₀+τ₁ c+τ₂ c ². Our results agree with the predictions of the Zimm model in the gel case but differ significantly for the sol state. Received: 25 May 1999 /Accepted in revised form: 27 July 1999     

Study of the Gelation Process of Polyethylene Oxidea–Polypropylene Oxideb–Polyethylene OxideaCopolymer (Poloxamer 407) Aqueous Solutions

The gelation process of polyethylene oxide_a–polypropylene oxide_b–polyethylene oxide_acopolymer (poloxamer 407) aqueous solutions is studied by means of FTIR spectroscopy, rheology, and differential scanning calorimetry (DSC). The C–O–C stretching bands of infrared spectra were found to shift toward higher wavenumbers with sol–gel transition, indicating that hydrogen bonding is not the driving force for gelation. Linear viscoelastic data provide an alternative method for gel point determination of these thermoreversible gels. The results obtained with this method are found to coincide with those obtained using DSC. Gel point temperatures determined by these methods are close to 14°C for 25% (w/w) poloxamer 407 solutions and 10°C for 30% (w/w) solutions. In gel state, the elastic modulus (G′) and dynamic viscosity (η*) are found to be concentration and temperature independent for temperatures ranging from 20 to 35°C. In light of our results, we suggest a mechanism of gelation based on micelles packing and entanglements.     

Calorimetric study of dissolution kinetics of phosphorite in diluted acetic acid

In this report, we present a thermodynamic and kinetic study of the selective dissolution of calcite from low-grade phosphate ores (Epirus area, Greece) by dilute acetic acid at isothermal conditions. A twin calorimeter with two identical membrane vessels, for the acid dissolution process, and for the reference was used. The curves of rate vs. time of the phosphorite dissolution for various temperatures show that the maximum (.q _max) was increased, whereas the time (t _peak) to achieve the corresponding .q _max values was decreased, as the experimental temperature was increased. The dissolution enthalpy was increased from 13.1 to 16.7 kJ mol⁻¹, as the experimental temperature was increased from 10.0 to 28.0°C. The chemical analysis of the supernatant solutions shows that the main process was the calcite dissolution. The reaction model with general form, ln(1/(1-X))=kt ^m, was found to fitted the experimental data regardless of the experimental temperature. These results were assigned in the presence of two different kinds of particles in the phosphorite. The activation energy of the dissolution process was found 69.7 kJ mol⁻¹. The SEM micrographs of acid dissolution samples showed two different textures after acid dissolution.     

Temperature dependence of volume changes on glycine-PEG and L-alanine-PEG in aqueous solution

The volume changes on mixing aqueous solutions of glycine-PEG and L-alanine-PEG were respectively measured with a vibration densimeter as functions of concentration and temperature. The volume changes ( _m)V for the glucine-PEG-H₂O system were positive, and these _v(x,m) values of different total molality almost linearly decreased with an increase in temperature and converged around 110°C by extrapolation. On the other hand, those for the L-alanine-PEG-H₂O system were almost zero and independent of temperature. It is considered that the influence of hydration cospheres on glycine-PEG interaction for the glycine-PEG-H₂O system disappears around 110°C.     

Solubility of sildenafil citrate in propylene glycol + water mixtures at various temperatures

The solubility of sildenafil citrate (SC) in aqueous mixtures of propylene glycol (PG) was investigated. This study was carried out at different mass fractions of PG ranging from 0.1 to 0.9 at T = 293.2–313.2 K. The solubility of SC in the mixed solutions increased with increasing temperature and PG mass fraction.

The solubility values were correlated by two co-solvency models (Jouyban–Acree model and van’t Hoff–Jouyban–Acree model). The mean relative deviations (MRD) were 5.7% and 5.5%, respectively. Density of the SC-saturated solutions over the entire solvent composition and temperature range was also measured and the results correlated with the Jouyban–Acree model. Furthermore, the apparent thermodynamic properties, dissolution enthalpy, dissolution entropy and Gibbs free energy change of dissolution process of SC in all the mixed solvents were calculated according to van’t Hoff and Gibbs equations. Dissolution of SC in these mixed solvents is an endothermic process.     

Interaction between Na+ and polymer in aqueous solution of sodium salts of poly(2-hydroxyethyl methacrylate-co-methacrylic acid) studied by 23Na-NMR

The interaction between Na⁺ and polymer was studied by ²³Na-NMR for the aqueous solution of P(HEMA-co-MAANa), sodium salt of poly(2-hydroxyethyl methacrylate-co-methacrylic acid), as a function of the polymer concentration, charge density of the polymer chain, and temperature. The NMR line width of ²³Na-NMR in 1% (w/v) aqueous solution of the P(HEMA-co-MAANa) narrowed with increasing temperature due to the rapid exchange of Na⁺ between free and polymer-bound states with a rate of exchange exceeding the quadrupolar relaxation rate in the latter state. At high concentrations of the polymer above 1.0% (w/v) at 298 K, the ²³Na-NMR relaxation fits for a single Lorentzian due to the rapid exchange between two Na⁺ states. However, it follows a biexponential decay of magnetization in dilute solutions of polymer. The biexponential decay character of relaxation increased with the increase of the fraction of the MAANa monomer unit on the polymer chain. This feature of ²³Na-NMR relaxation was used to deduce the correlation time (τ_c), the degree of binding (p_B), and the quadrupole coupling constants (X) of the polymer-bound counterion. The χ and τ_c values show that the mobilities of the polymer chain are correlated with the motion of Na⁺ in aqueous solution of the polymer and there is a small degree of the specific binding between COO^? and Na⁺. No evidence in support of the intramolecular conformational change by the charge density variation in P(HEMA-co-MAANa) was obtained. © 1993 John Wiley & Sons, Inc.     

Modified carrageenan. 5. Preparation,swelling behavior,salt‐ and pH‐sensitivity of partially hydrolyzed crosslinked carrageenan‐graft‐polymethacrylamide superabsorbent hydrogel

The polysaccharide, kappa‐carrageenan (κC) was chemically modified to achieve a novel superabsorbent hydrogel via graft copolymerization of methacrylamide (MAM) onto the substrate followed by alkaline hydrolysis. Ammonium persulfate (APS) and N,N′‐methylene bisacrylamide (MBA) were used as a free‐radical initiator and a crosslinker, respectively. The saponification reaction was carried out using sodium hydroxide aqueous solution. Either κC‐g‐PMAM or hydrolyzed κC‐g‐PMAM (PMAM: polymethacrylamide) was characterized by FT‐IR spectroscopy. The effect of grafting variables (i.e. concentration of MBA, MAM, and APS) and alkaline hydrolysis conditions (i.e. NaOH concentration, hydrolysis time and temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. The swelling capacity of these hydrogels was also measured in various salt solutions. Results indicated that the swelling ratios decreased with an increase in the ionic strength of the salt solutions. This behavior can be attributed to charge screening effect for monovalent cations, as well as ionic crosslinking for multivalent cations. Absorbency of superabsorbing hydrogels was examined in buffer solutions with pH range 1–13. Also, the pH reversibility and on–off switching behavior, at pH values 3.0 and 8.0, makes the synthesized hydrogels good candidates for controlled delivery of bioactive agents. Finally, swelling kinetics in distilled water and various salt solutions was preliminary investigated. Results showed that the swelling in water was faster than in saline solutions. Copyright © 2004 John Wiley & Sons, Ltd.