Helmut Auweter

Kinetics of adsorption of polyvinylamine on cellulose fibers: II. Adsorption from electrolyte solutions

Adsorption from electrolyte solutions of fully hydrolyzed polyvinylamine on cellulose fibers was investigated by supplying the polymer to the fibers at controlled rate. This was implemented by employing a reactor only open to the fluid in which the fiber dispersion were confined and homogenized. The adsorbed layers may be defined as diffuse or dense layers. Diffuse layers are characterized by a surface coverage limited to 0.65 mg/g cellulose in salt-free solutions. Addition of NaCl or CaCl(2) to the fiber dispersion and the polymer solution promotes the adsorption rate and increases the amount of adsorption to 1.5 mg/g cellulose. For dense polymer layers, for which the coverage amounts to values close to 10 mg/g cellulose in salt-free systems, addition of electrolyte does not change the kinetic and adsorption characteristics. Insofar as the variation of the molecular areas of the polymer within the diffuse layers as a function of the ionic strength parallels the variation of the molecular characteristics of solute molecules, the formation of diffuse layers is expected to proceed by random deposition of solute molecules which later individually sustain strong reconformation. Adsorption isotherms show a limited influence of the ionic strength. Obviously, the passage from dense layers of high surface coverage to low adsorption values at equilibrium requires extended reconformation of adsorbed macromolecules and desorption of a great part of the molecules already adsorbed.

Highly concentrated emulsified microemulsions as solvent-free plant protection formulations

Effective plant protection agents are readily available and well implemented in industry. However, delivery to the plant and application on the leaf are processes that still need to be optimized. Up to now plant protection formulations represent either emulsion or suspension concentrates that often contain environmentally harmful organic solvents and/or adjuvants. Emulsified microemulsions are hierarchically organized systems comprising emulsion droplets that confine a water-in-oil microemulsion. In the present contribution we show that emulsified microemulsions prepared from environmentally friendly components can be loaded with the plant-protection agent Fenpropimorph® up to 48 wt.% without organic solvent. The emulsion itself is highly concentrated, containing 60 wt.% of dispersed phase, and can be readily diluted with water for spraying in farming applications. Small-angle X-ray measurements reveal the existence of a water-in-Fenpropimorph® microemulsion confined inside the emulsion droplets. Dynamic light scattering shows that the emulsions prepared are monomodal, comprising droplet radii in the hundred nanometer range.

Reconformation of polyvinylamine adsorbed on glass fibers.

Surface area exclusion chromatography was used to investigate the reconformation of fully hydrolyzed polyvinylamine. The polymer is adsorbed on stacked glass fiber filters constituting the stationary phase while the polymer solution is injected at the inlet of the chromatography column. From numerical simulation and experimental chromatograms of nonreconforming polyelectrolytes, the amount of polymer adsorbed per filter represented as a function of the filter position along the column (the histogram) was determined to be continuously decreasing and not to depend on the rate of elution. For polyvinylamine, the histograms are peaked and the height of the peak was determined to depend greatly on the rate of polymer supply to the column that was controlled by monitoring the polymer concentration and/or the rate of elution (mass-transfer-controlled adsorption). Modifications in the adsorption on the successive filters were converted into changes in the interfacial area of adsorbed molecules taking into account model histograms as well as experimental adsorption histograms of non reconforming systems. Macromolecule concentration in the mobile phase and contact time between solute and adsorbed molecules were determined to be the two parameters controlling the extent of polymer desorption. The unusual shape of the histogram thus was attributed to reconformation of the adsorbed polymer, which was stimulated by interfacial exchange between segments belonging to trains of adsorbed macromolecules and chain segments of solute ones.

Relaxation phenomena of hydrolyzed polyvinylamine molecules adsorbed at the silica/water interface: II. Saturated heterogeneous polymer layers

Surface area exclusion chromatography (SAEC) was employed to determine the individual relaxation of polymer molecules within a saturated heterogeneous layer composed of two polymers of different molecular characteristics. The investigations focused on three systems differing in molecular weight and/or hydrolysis grade. The molecular relaxation process was determined to be different within the heterogeneous layer when compared with the behavior of the same polymer in the homogeneous layer. The modifications in the relaxation process of a given polymer were imposed by the interfacial characteristics of the second polymer. Finally, in heterogeneous layers, the relative variation of the interfacial area of the two polymers is expressed in a single relationship.

Effects of poly- and monodisperse surfactants on14C-epoxiconazole diffusion in isolated cuticles of Prunus laurocerasus

BACKGROUND Surfactants are known to enhance the foliar uptake of agrochemicals. It was the aim of this study to compare the enhancing effect of three polydisperse surfactants (Brij 30, Plurafac LF300 and Wettol LF700) and five monodisperse alcohol ethoxylates (C12 E3, C12 E4, C12 E5, C12 E6 and C12 E8) on (14)C-epoxiconazole diffusion in cuticles isolated from cherry laurel (Prunus laurocerasus L.). RESULTS Rate constants (k*) of (14) C-epoxiconazole diffusion were measured in the presence and in the absence of the surfactants. Polydisperse surfactants increased the rates of foliar penetration of (14) C-epoxiconazole by factors of between 8 and 16. With monodisperse surfactants, enhancing effects on cuticular penetration were 2-16-fold. Effects were highest with alcohol ethoxylates of intermediate size, whereas they were lower for the smaller, more lipophilic and the larger, more polar monomers. In addition, diffusion of four monodisperse alcohol ethoxylates (C12 E3, C12 E4, C12 E5 and C12 E6 ) across cuticles was measured. Rate constants of alcohol ethoxylates decreased with decreasing lipophility and increasing molecular weight. CONCLUSION The results indicate that enhancement of foliar penetration across cuticles by surfactants was most efficient when both (14)C-epoxiconazole and surfactants had similar mobilities in the transport-limiting barrier of the cuticles. This observation should be of interest in future strategies to optimise foliar uptake of agrochemicals using surfactants.