Swelling pressure equilibrium of physical networks in the field of an analytical ultracentrifuge

Investigations of the swelling pressure equilibria of a physical network are performed with an analytical ultracentrifuge. The advantage of this method is that in contrast to the known swelling pressure instruments, swelling pressures in a range of composition are obtained from only a single equilibrium experiment. The Schlieren optical system of the ultracentrifuge allows the observation of the concentration gradient during the process of deswelling and swelling, and furthermore, the detection of the gel concentration at every point. The system gelatin/water shows a different behavior than that expected from the theory of Flory-Huggins for a swollen random network. The measured curves of concentration vs. the swelling pressure intersect each other in case of low initial concentrations. This shows that these networks are inhomogeneous. A new method to measure and evaluate the Schlieren pattern is described.This paper was presented at the VI. Symposium on Analytical Ultracentrifugation, Marburg, FRG, February 16–17, 1989.     

Phase diagrams and structures of lecithin/water systems with branched lecithin components

The influence of chain branching on the phase transition parameters and structures of the homologous series of 1-(x-methylpalmitoyl)-2-hexadecyllecithins in the water-saturated two-phase region (50 wt.% water) were studied by differentialscanning-calorimetry as a function of the position x of methyl branching. With increasing x a linear decrease in the enthalpies and alternating temperatures of main transition were observed. The phase diagram of the ternary system 1-(3-methyl-palmitoyl)-2-hexadecyllecithin/1,2-dipalmitoyllecithin/water (50 wt.% water) showed that both components are completely miscible within the high-temperature phase (L -phase). However, in the low-temperature phase (gel phase), the components are partially miscible only. It follows that gel phases with interdigitated chains and those with tilted chains are not completely miscible. The phase diagram of the ternary system 1,2-di-(8-methylpalmitoyl)-lecithin/1,2-dipalmitoyllecithin/water (50 wt.% water) showed that both components are completely miscible within the high-temperature phase and low-temperature phase. Within the concentration range between the mole fraction x=0.91 and x=0.97, a drop-like course in the phase diagram was obtained.     

Preparation of micron-size monodisperse polymer particles having highly crosslinked structures and vinyl groups by seeded polymerization of divinylbenzene using the dynamic swelling method

Micron-size monodisperse polystyrene/polydivinylbenzene (PS/PDVB) composite particles having highly crosslinked structures and vinyl groups were prepared as follows. First, 1.9 m-size monodisperse PS seed particles produced by dispersion polymerization were dispersed in ethanol/water (70/30, w/w) solution which dissolved divinylbenzene (DVB) monomer, benzoyl peroxide as an initiator and poly(vinyl alcohol) as a stabilizer. The PS seed particles were swollen with a large amount of DVB monomers to 4.3 m in diameter while keeping good monodispersity by the dynamic swelling method, where water was slowly added, continuously, with a micro feeder into the dispersion. And then, the seeded polymerization of the absorbed DVB was carried out.Part CXXXV of the series Studies on Suspension and Emulsion     

Swelling of poly(methacrylic acid) gels and adsorption of L-lysine and its polymer on the gels

Poly (methacrylic acid) gels (PMAA gels) of various degrees of crosslinking were prepared and the dissociation behavior of these gels was examined; the swelling behavior was investigated as a function of the solution pH values. A reentrant phenomenon of swelling was observed and interpreted based on the Flory-Huggins equation and the Donnan equilibrium formula. Moreover, adsorption of L-lysine, oligo(L-lysine)s (Lys-n,n=3, 9, and 19) and poly(L-lysine) onto PMAA gels from aqueous solutions was investigated under different conditions of pH and concentration of adsorbate. The adsorption ratio of L-lysine onto PMAA gel is dependent on both the pH of solution and the degree of crosslinking. In a pH range between 8 and 9, the protonated form of L-lysine is strongly adsorbed on the PMAA gel by electrostatic interactions. Oligomers and polymer of L-lysine are adsorbed in a somewhat different way from the monomeric L-lysine. In addition, the desorption behavior of L-lysine from PMAA gels by a change in pH was also investigated.     

Thermotropic gelation of ovalbumin 1. Viscoelastic properties of gels as a function of heating conditions and protein concentration at various pH values

A study has been undertaken of stress relaxation in ovalbumin thermotropic gels with a concentration of 8–20%, depending on time and temperature of heating (respectively, 20–60 min, 70°–110°C), at pH 2.5–10.0. In all instances, the dependence of the initial gel elasticity modulus on heating has a single maximum. Gelation conditions corresponding to this maximum are considered optimal. Optimal gelation time is 30 min, regardless of pH. On the other hand, the optimal heating temperature depends on pH. To the right and left of the isoelectric point of protein (2.5pH<4.0 and 5.5G) of gels on heating conditions, pH and protein concentration (X ₁,X ₂,X ₃,X ₄), as well as on time of relaxation (t) may be generally described asG(X ₁,X ₁,X ₁,X ₁,t)=G _e(X ₁,X ₂,X ₃,X ₄)f(t), whereG _e is the equilibrium value of the elasticity modulus, and f(t) the relaxation function. Thus, a change in the parameters only affects the value of the equilibrium elasticity modulus, and exerts no effect on the relaxation time spectrum. For this reason, all the relaxation curves obtained may be transformed into two normalized relaxation functions:f(t)=f(t)/f(1)=G(X ₁,X ₂,X ₃,X ₄,t)/G(X ₁,X ₂,X ₃,X ₄, 1)Each of these normalized functions corresponds to one of the homologous groups. Rheological similarity of gels in each homologous group evidently points to their structural similarity. Invariance of the gel relaxationproperties with regard to protein concentration, leads to a concentration dependence of the equilibrium modulus at various pH values. These dependences are curvilinear on a double logarithmic scale. The slope of the curve exceeds 2 in the entire concentration interval studied. In other words, the dependences obtained cannot be described by the usual law of squares. On the other hand, they adequately match Hermans theoretical relation for a network formed by random association of identical polyfunctional particles without cyclization. This simple model evidently gives a true picture of the major regularities of thermotropic gelation for ovalbumin. An agreement between this theory and experiment was achieved for a protein concentration ofC ^*=6.0±1.0% at the gel point regardless of pH. Invariance of gelpoint position with regards to pH demands further confirmation.List of symbols T _h,t _h heating temperature and time - T _h ^* ,t _h ^* optimal heating temperature and time - C protein concentration - C ^* protein concentration in gel-point - G relaxation modulus - G _e equilibrium modulus - f(t) relaxation function - t time of relaxation - f(t) normalized relaxation function - fT _A (t), f _B (t) normalized relaxation functions of groups A and B - G ₁ T _h,t _h-reduced modulus - G ₂ T _h,t _h, pH-reduced modulus - G ₃ C-reduced modulus - b ₁ T _h, t_h reduction parameter of modulus - b ₂ pH reduction parameter of modulus - b ₃ C reduction parameter of modulus - W_g gel-fraction     

Time domain dielectric spectroscopy. A new effective tool for physical chemistry investigation

The general principles of time domain dielectric spectroscopy (TDS) are summarized. The methods of data treatment and presentation, and different TDS methods which enable one to obtain the permanent spectrum of ^* () in the frequency range of 10⁵–10¹⁰ are given. The examples of TDS application for the investigation of dielectric properties in samples of different nature and structure are considered in this review.     

Effect of random copolymerization on growth transition and morphology change in polypropylene

The growth rate of an ethylene-propylene random copolymer with a 2.8% w/w ethylene content was studied in a similar manner to polypropylene. A growth regime transition associated with a birefringence change was observed at 130C, while the same phenomena appeared at 138C in isotactic polypropylene. In both polymers positive birefringence corresponds to Regime III, whereas negative birefringence of spherulites is associated with Regime II. The birefringence change is attributed to a change in the organization of crystalline lamellae: quadritic arrays of intercrossing lamellae at low temperature (Regime III) and preferentially radiating lamellae at higher temperature (Regime II). We confirm that such a morphological change can be interpreted using the concept of non-adjacent re-entry introduced in Hoffman's kinetic theory. Thus, quadritic morphology seems to have a partly kinetic origin. The shift of the transition temperature in the copolymer is due to the rejection of ethylene segments at the surface of crystalline lamellae of polypropylene.     

Surfactant-free emulsion polymerization of styrene using crosslinked seed particles

The aim of this research was to prepare a monodisperse polystyrene latex without surfactants adsorbed at the particle surface. Conventional polymerization formulations usually lead to large amounts of oligomers. Furthermore, they are characterized by a low reproducibility with respect to particle size. This was overcome by using a seed latex that was crosslinked in order to overcome dissolution in the monomer phase. By adjusting the seed concentration, any desired particle size in the range 0.5–1.2 m could be obtained. The monodispersity was very good.     

Production of anomalous polymer microspheres having uneven surfaces by “stepwise” heterocoagulation technique

Anomalous polymer microspheres having uneven surfaces were produced by stepwise heterocoagulation technique of small polymer particles (SPs) onto large polymer particles (LPs).SPs andLPs have surface charges opposite to each other in the emulsion states.SPs were produced by emulsion copolymerization of styrene and methacryloyloxyethyltrimethylammonium chloride, andLPs by emulsion terpolymerization of styrene, butyl acrylate and methacrylic acid, with nonionic emulsifier being used in both cases. Maximum covering ofLP bySPs was obtained under the conditions that both emulsions were blended without the coagulation at pH 3 at room temperature and then left stand to coagulate with each other at 70 °C for 4 h at pH 9.Part CXI of the series Studies on Suspension and Emulsion.     

The behaviour of drag-reducing cationic surfactant solutions

The behaviour of two types of drag reducing surfactant solutions was studied in turbulent flows in pipes of different diameters. Our surfactant systems contained rod-like micelles; they consisted of equimolar mixtures ofn-tetradecyltrimethylammonium bromide,n-hexadecyltrimethylammonium bromide, and sodium salicylate. The structure of the turbulence was studied using a laser-Doppler anemometer in a 50 mm pipe. In the turbulent flow regime both surfactant solutions exhibited characteristic flow regimes. These flow regimes can be influenced by changing the amount of excess salt, the surfactant concentration, or the temperature. Shear viscosity measurements in laminar pipe and Couette flows show the occurrence of the so-called shear-induced state, where the viscosity increases and the surfactant solution becomes viscoelastic. The shape of the turbulent velocity profile depends on the flow regime. In the turbulent flow regime at low Reynolds numbers, velocity profiles similar to those observed for dilute polymer solutions are found, whereas at maximum drag reduction conditions more S-shaped profiles that show deviations from a logarithmic profile occur. An attempt is made to explain the drag reduction by rod-like micelles by combining the results of the rheological and the turbulence structure measurements.     

Theory of swelling of a crosslinked substance in equilibrium with a solvent in various phases

In this paper the thermodynamic theory of a body in a liquid, crystalline or vaporized solvent is treated. The equilibrium swelling curves are discussed for the different states of the solvent. The slopes of the swelling curves are dependent on the differential enthalpy of dilution of the solvent and, additionally, on the enthalpies of vaporization, crystallization and sublimation of the solvent related to the state of the swelling agent. The slopes of the swelling curves are determined by the differential heat of vaporization, the differential heat of solution of the solvent or the differential heat of fusion according to the state of the swelling agent. Directly below the melting pointT _m,1, or directly above the boiling pointT _b,1 of the solvent the swelling curves change their slopes with a sharp bend. This phenomenon can be used to determine (₁/w ₁) at constant temperature and pressure, which means the change of the chemical potential ₁, with the change of the weight fractionw ₁ of the solvent. Using a simplified statistical thermodynamic relation it is possible to describe the principal courses of the swelling curves in all states of the solvent.     

Interfacial effects on the ageing behavior of high density polyethylene filled with glass spheres

The stress relaxation and creep behavior of unfilled high density polyethylene (HDPE) and HDPE filled with untreated and surface-treated glass spheres were measured at room temperature. A silane-based coupling agent capable of providing a covalent bond between HDPE and the glass spheres was used for the surface-treatment. Two different amounts of the coupling agent were employed giving silane layers on the fillers with different thicknesses. The effect of ageing time at room temperature on the viscoelastic properties after quenching from 100 °C to room temperature in ice water was also investigated. The effects of the surface treatment of the fillers and the ageing time was characterized by means of the internal stress ( _i ) concept. The _i -value increased with the degree of interaction of the filler/matrix interface and the ageing time. It was here not possible to superimpose the different flow curves with regard to the ageing time with sufficient accuracy. This is due to the variation of _i with ageing time. The surface-treatment of the filler had a marked effect on the creep behavior at high applied stress levels and on the ageing behavior of the composites, presumably due to the formation of an interphase region close to the filler surface with different properties and different ageing characteristics than that of the bulk of the matrix.     

Production of anomalously shaped carboxylated polymer particles by seeded emulsion polymerization

Anomalous polymer particles with a partial protuberance like octopus ocellatus were produced under alkaline conditions by seeded emulsion copolymerization for styrene and butyl acrylate, with styrene-butyl acrylate-methacrylic acid terpolymer emulsion as seed. The mechanism of production of the polymer particles was studied. By transmission electron microscopic observation of the particles at each conversion, it was observed that the anomalous polymer particles were produced by partial growth of each of the individual seed particles throughout polymerization. Ionization of the carboxyl groups and low viscosity in the growing particles during the process of polymerization were important factors for partial growth.Part CIII of the series Studies on Suspension and Emulsion.     

Solutions of alkali soaps and water in fatty acids XIII. Circumstances that regulate the extension of theL 2-phase and the role of the acid-soaps rich in fatty acid for the occurrence of the phase

A basic requirement for that type ofL ₂-phase which exists in the system sodium octanoate-octanoic acid-water is the formation of acid-soaps. In order for the phase to be formed at all, the temperature must lie above the melting point of the fatty acid so that a reaction in non-aqueous milieu between neutral soap and fatty acid is possible. In order to obtain the characteristic shape and complete extension of the phase in direction of high water content the temperature must be so high that also the hydrated acid-soaps occur in fluid state. On the other hand the temperature cannot be so high that the acid-soaps become unstable.At temperatures at which the phase has obtained its full extension those circumstances differs which in different regions regulate the location of the phase borders; they depend on the composition of the acid soaps and on their amounts. In that part of the phase where the molar ratio between octanoic acid and sodium octanoate lies between 2 and 3 and where one has a continuous transition from reversed to normal structure only the two acid octanoates 1 NaC₈ 2 HC₈ x H₂O and 1 NaC₈ 3 HC₈ x H₂O occur and both are at 20 °C in fluid state.At water contents from about 22 % to 40 % the hydrate-water molecules belonging to the first mentioned soap are capable of contributing actively to the formation of large aggregates of acid-soap, a process which however is counteracted by the inmixing of the latter acid-soap. This mixture of the two acid-soaps decides in this region where the border of the phase will lie in direction towards an increased content of sodium octanoate; the result is that in spite of the fact that the hydration is increased, the border is only slowly displaced towards a higher content of fatty acid. As soon as the hydration of the acid octanoates has been completed and the additional water occurs as unbound bulkwater, the location of the phase boundary will no longer be influenced by the water content — now it will be the amphiphilic composition of the acid-soaps that determines the location of the border and it remains at the molar ratio 2.5 between octanoic acid and sodium octanoate at water contents from about 40% and up to 82%.In the direction of decreasing content of neutral sodium octanoate and increased content of water theL ₂-phase both at the highest content of fatty acid and the highest contents of water will be in equilibrium with the water-richL ₁-phase; in the first mentioned region with theL ₁-phase below the lac where at the border it is saturated with octanoic acid and in the latter region with theL ₁-phase just above the lac, where the dilute sodium octanoate solution contains dissolved 1 NaC₈ 1HC₈ x H₂O. In the large central part of theL ₂-phase, from about 20 % to about 86 % of water, the location of the border is dominated by the acid octanoate 1 NaC₈ 3 HC₈ x H₂O and that makes an equilibrium with theL ₁-phase impossible; instead one has an equilibrium via a two-phase zone between the amphiphile-rich region of theL ₂-phase and its water-rich region. In the first region the location of the border is regulated by the decreasing capability of the hydrated acid octanoate 1 NaC₈ 3 HC₈ x H₂O to dissolve octanoic acid; in the latter it is regulated by the fact that 1 NaC₈ 3 HC₈ x H₂O is the most fatty acid-rich acid-soap that is formed and that the octanoic acid is very little soluble in water and in the aqueous solution of this acidsoap.The middle part of theL ₂-phase, especially the region between about 55 % and 82 % of water, constitutes a direct continuation of the liquid crystalline lamellarD-phase. The liquid crystalline character of theD-phase is lost at the transition, but the lamellar organization is retained. That the molecules at least up to a water content of about 40 % are of the original reversed type and have an elongated shape with a central part of hydrated polar groups, from which core the hydrocarbon chains extend in two opposite directions, is the reason to that they, at crowding, form transient layer-like agglomerates of tightly packed more or less parallel molecules; this facilitates the transformation to coherent double amphiphilic layers, in which all molecules lie with the hydrated polar groups outwards toward coherent domains of bulk-water, without another liquid phase occurs.     

Effect of thick fixed-charge layers on electrostatic interaction — a theoretical approach

The electrostatic interaction pressure of charged surface layers is considered qualitatively and quantitatively. In the case of mutual penetration of the surface layers in addition to Maxwell stress and osmotic resp. hydrostatic pressure an isotropic stress on the fixed charges carrying molecules of the surface layers has to be taken into account. The derivation of the pressure-distance equations is given starting from both thermodynamic/electrostatic and hydrostatic/electrostatic principles. A possible biological significance of the additional stress is discussed emphasizing its role in modifying the structure of surface layer molecules.List of symbols e ₀ elementary charge - k Boltzmann constant - n _i concentration of theith ionic species in the bulk solution - P hydrostatic pressure - P hydrostatic pressure in the bulk volume (× ) - P ^h integration constant, independent on ×:P ^h =P(h) - T absolute temperature - Z _i electrovalence of theith ionic species - thickness of the surface layer - , ₀ relative and absolute permittivities - II(×) osmotic pressure at position × - II osmotic pressure in the bulk solution (× ) - osmotic pressure in the symmetry plane of interacting identical surface layers (electric field strength equals zero) - integration constant, independent on ×: - _e ^h electrostatic component of the disjoining pressure _e ^h = _e (h) - (×) mobile charge density profile (cations and anions of the electrolyte) - (×) fixed charge density profile - ^t(x) total charge density profile ( ^t = +) - ¹(x) fixed charge density profile of one of the two surface layers ( ¹(×) 0 for 0×) - (×) electric potential profile     

Solutions of alkali soaps and water in fatty acids. XII. Correlations between the acid sodium octanoates in the isotropic liquidL 2-phase at water contents from 82% down to 10% and those in adjacent liquid crystalline phases

A close connection exists between the isotropic L₂-phase and the liquid crystalline lamellar D-phase. This connection is evidenced both with respect to similar compositions of their acid sodium octanoates and concerning the structure of the phases.The two-phase zone between these phases is very narrow, from 82 % down to about 55 % of water, it then widens slowly to about 40 % and thereafter very rapidly to 22 % of water; below the latter value it remains broad. The border of the L₂-phase is in the whole region from 82 % to 22 % of water located at molar ratios between octanoic acid and sodium octanoate of somewhat above 2.0; the border of the D-phase lies at the same values down to a water content of 40 %. The acid octanoate 1 NaC₈ 2 HC₈ x H₂O plays thus a considerable role in the phase transition all the way down to a water content of 22 %. As long as free bulk-water exists in both phases the structures in them remain alike; this similarity is greatest as long as the amount of bulk-water is so large that it suffices to form coherent domains. At contents of water below 40 %, that is after the disappearance of the bulk-water and when a decrease in the content of water begins to affect the hydration of the acid octanoates, the structural similarity between the phases disappears rapidly.     

The acceleration of decomposition of potassium persulfate in the presence of sodium dodecyl sulfate and polymer particles as a model of emulsion polymerization system

The decomposition rates of potassium persulfate (KPS) in aqueous solutions containing sodium dodecyl sulfate (SDS) in the presence of polystyrene or poly(methyl methacrylate) particles as models of emulsion polymerization systems were measured by isotachophoresis. Free SDS molecules dispersed in the monomolecular state had an ability to accelerate the KPS decomposition, but SDS molecules adsorbed onto the polymer particles did not accelerate it.Part CXX of the series of Studies on Suspension and Emulsion     

Gas permeability of block copolymers of styrene and butadiene

The permeability of styrene-butadiene block copolymer foils with different composition prepared by casting and pressing has been investigated for the gases Ar, CO₂, and CH₄ at pressure difference of 400 mbar and at the temperature range 298 T [K] 333.The permeation process can be described by the solution diffusion mechanism. The diffusion coefficients decrease in the sequence of the gases Ar, CO₂, and CH₄ and the solubility coefficients increase in the sequence Ar, CH₄, CO₂.The dependence of the permeability on the composition of the block copolymer can be interpreted by the help of percolation theory and the effective medium theory. It follows the critical volume fraction of the percolation of the transport phase _PB ^c (= 0,23) and the coordination numberz (= 4) giving an information concerning the multiphase structure of the block copolymer.Presented in part at the 33^rd Annual Meeting of the Colloid-Gesellschaft, Graz, Austria, September 14–16, 1987.     

Dielectric properties of moist CaCO3 filled polyethylene composites

The capacitance and the dielectric loss tangents of CaCO₃ filled polyethylene composites were studied. Composite samples, prepared by polymerizing ethylene on the surfaces of fillers, pre-treated by polymerization catalysts, were compared to normal mechanical mixtures. Dielectric dispersion,, and loss, , proved to be sensitive to heating or vacuum treatment. Investigation of samples under conditions of different relative humidities showed that the dielectric dispersion is due to adsorbed water. Both and increased with decreasing frequency and the ratio of loss and dispersion was nearly constant. Dielectric data measured at different relative humidities could be represented by a single Cole-Cole plot. Samples soaked in water for different periods yielded qualitatively similar but quantitatively different Cole-Cole plots. Composite samples showed higher losses at similar humidities.Possible interpretations in terms of a molecular relaxation model, an interfacial relaxation model, including a charged double layer mechanism, percolation theory and the universal response theory were examined, but none was able to fully explain the observed phenomena.     

Electrolytic conductivity of poly(1,3-propylene phosphate) solutions containing mono- and divalent-counterions

The results of conductivity measurements for aqueous solutions of poly(1,3-propylene phosphate) (PPP), which can be considered as a synthetic analogue of naturally occurring teichoic acids, are reported. Experiments were carried out with oligomeric fractions of a polymer in acidic, sodium, potassium, magnesium and calcium forms. The concentration and molecular weight dependence of the equivalent conductivity of PPP was analysed and the limiting equivalent conductivity determined. From the conductivity data, the polyion-counterion interaction parameter F and the equivalent conductivity of a polyion _p were calculated. It was shown that both F and _p depend on polyelectrolyte solution concentration and molecular weight of PPP. Conclusions concerning mono- and divalent metal ions binding to PPP are drawn.