Adhesive liquid-crystalline polymers

The synthesis and characterization of liquid-crystalline polymers with possible good adhesive properties is reported. These polymers are prepared by alternating copolymerization of maleic anhydride and mesogenic alkenes. The spacer length m is varied (m = 2, 3, 4, 6, 8 and 9) and methoxybiphenyl is used as the mesogenic group. The glass transition temperature decreases and the isotropization temperature increases with spacer length. Depending on the spacer length and temperature, S_B and S_Ad mesophases can be observed. After annealing, spin-coated films of these polymers show very regular layered structures with a layer spacing similar to that in the bulk.     

Polymer adsorption and its effect on the stability of hydrophobic colloids

Summary As a first step in a study on the interaction between polymers and hydrophobic colloids we investigated in detail the adsorption of polyvinyl alcohol (PVA) on aqueous silver iodide sols. The adsorption is irreversible. Adsorption isotherms are of the highaffinity type. The amount adsorbed increases with molecular weight and with the fraction of acetate groups in the PVA chain. The effective thickness of the adsorbed layer was determined viscosimetrically and independently checked by an electrophoretic method. Double layer studies enabled the determination of the occupancy of the first layer on the surface by polymer segments. It was found that even at maximal coverage with polymer this layer is still about 30% void. The combination of these data enabled the assessment of the polymer segment distribution. It was found that with not too low coverages the distribution isHoeve- like. The distribution, thus obtained reflects itself in the flocculation of AgI sols by PVA.Presented at the 25th Colloid-Meeting in Munich, October 13–15, 1971     

Numerical modeling of the forming of fiber bundles from polymer melts

A mathematical model for the process of forming of synthetic fibers moving as a bundle is formulated. Three main versions are considered: forming of exposed bundles, forming in shafts with blowing, and stretching of fibers by means of an ejector. Low and high-speed forming regimes are also considered within the framework of the Maxwell model of a viscoelastic fluid. The calculations performed showed that the parameters of the fiber bundle produced depend on the method of forming used and on the local conditions in high-speed stretching, accompanied by oriented crystallization. Dnepropetrovsk State University, Dnepropetrovsk 320625. Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 40, No. 1, pp. 184–192, January–February, 1999.     

Asymptotic method for solving problems with radial laminar jets of immiscible liquids

Two problems involving radial laminar jets of immiscible liquids are considered: a free radial slit jet and a jet on a rotating disk. An asymptotic method of solution is proposed that makes it possible to determine the flow parameters far from the source. The difference between these flows and those of homogeneous liquids is demonstrated.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 3, pp. 192–28, May–June, 1980.     

Preparation and characterization of polymer single crystals for use as adsorbent

Single crystals of polyoxymethylene are flat, homogeneous, and essentially uncharged and offer a large specific surface area. Since they can be prepared reproducibly and in large amounts, they constitute a suitable model substrate in systematic adsorption studies. The crystallization procedure is discussed in some detail. The thickness of the crystals is obtained from EM and SAXS measurements, the results being in excellent mutual agreement. Combining this thickness with the crystal density the geometrical surface area is found to be 150 m²/g. This is compared with the surface area obtained by BET analysis of nitrogen adsorption (30 m²/g) and with the surface area that follows from adsorption of polyoxyethylated nonyl phenols from aqueous solution (60 m²/g). The discrepancy in the results is explained in terms of different degrees of aggregation of POM crystals in the dry state and in suspension. Finally, some preliminary results of albumin and sodium polystyrene sulfonate adsorption are discussed.     

When tethered chains meet free ones; the stability of polymer wetting films on polymer brushes

We present a combined experimental and theoretical self-consistent field (SCF) investigation of the wetting behavior of a polystyrene melt (composed of chains with degree of polymerization P) on top of a polystyrene brush (composed of chains with length N) grafted onto a silica surface. The control variables are the grafting density σ of the brush chains and the length of mobile chains P. Experiments show in agreement with the theory that there is a window of complete wetting. Both at very low and at high grafting densities the system remains partial wet. At large degree of polymerization P, there is a difference between the experimental and theoretical results. Theory predicts partial wetting only, whereas the window of complete wetting persists in the experiments even when P >> N. This difference is attributed to the double-well structure of the disjoining pressure as revealed by the SCF theory. With this type of disjoining pressure it is conceivable that a metastable zero contact angle remains present for very long times.     

Analytical phase diagrams for colloids and non-adsorbing polymer

We review the free-volume theory (FVT) of Lekkerkerker et al. [Europhys. Lett. 20 (1992) 559] for the phase behavior of colloids in the presence of non-adsorbing polymer and we extend this theory in several aspects: (i) We take the solvent into account as a separate component and show that the natural thermodynamic parameter for the polymer properties is the insertion work Pi(v), where Pi is the osmotic pressure of the (external) polymer solution and v the volume of a colloid particle. (ii) Curvature effects are included along the lines of Aarts et al. [J. Phys.: Condens. Matt. 14 (2002) 7551] but we find accurate simple power laws which simplify the mathematical procedure considerably. (iii) We find analytical forms for the first, second, and third derivatives of the grand potential, needed for the calculation of the colloid chemical potential, the pressure, gas-liquid critical points and the critical endpoint (cep), where the (stable) critical line ends and then coincides with the triple point. This cep determines the boundary condition for a stable liquid. We first apply these modifications to the so-called colloid limit, where the size ratio q(R)=R/a between the radius of gyration R of the polymer and the particle radius a is small. In this limit the binodal polymer concentrations are below overlap: the depletion thickness delta is nearly equal to R, and Pi can be approximated by the ideal (van't Hoff) law Pi=Pi(0)=phi/N, where phi is the polymer volume fraction and N the number of segments per chain. The results are close to those of the original Lekkerkerker theory. However, our analysis enables very simple analytical expressions for the polymer and colloid concentrations in the critical and triple points and along the binodals as a function of q(R). Also the position of the cep is found analytically. In order to make the model applicable to higher size ratio's q(R) (including the so-called protein limit where q(R)>1) further extensions are needed. We introduce the size ratio q=delta/a, where the depletion thickness delta is no longer of order R. In the protein limit the binodal concentrations are above overlap. In such semidilute solutions delta approximately xi, where the De Gennes blob size (correlation length) xi scales as xi approximately phi(-gamma), with gamma=0.77 for good solvents and gamma=1 for a theta solvent. In this limit Pi=Pi(sd) approximately phi(3gamma). We now apply the following additional modifications: With these latter two modifications we obtain again a fully analytical model with simple equations for critical and triple points as a function of q(R). In the protein limit the binodal polymer concentrations scale as q(R)(1/gamma), and phase diagrams phiq(R)(-1/gamma) versus the colloid concentration eta become universal (i.e., independent of the size ratio q(R)). The predictions of this generalized free-volume theory (GFVT) are in excellent agreement with experiment and with computer simulations, not only for the colloid limit but also for the protein limit (and the crossover between these limits). The q(R)(1/gamma) scaling is accurately reproduced by both simulations and other theoretical models. The liquid window is the region between phi(c) (critical point) and phi(t) (triple point). In terms of the ratio phi(t)/phi(c) the liquid window extends from 1 in the cep (here phi(t)-phi(c)=0) to 2.2 in the protein limit. Hence, the liquid window is narrow: it covers at most a factor 2.2 in (external) polymer concentration.     

Polymeradsorption und ihre Wirkung auf die Stabilit?t hydrophober Kolloide. III. Kinetik der Ausflockung von Silberiodid-Solen

Ohne Zusammenfassung