Corona stretching

It is important to define clearly the characteristic features of block copolymer micelles. We mentioned above that the insoluble blocks formed a micellar core surrounded by a corona. Depending on the composition of the starting block copolymer, two limiting structures can be drawn (1) starlike micelles with a small core compared to the corona and (2) crew-cut micelles with a large core and highly stretched coronal chains. Both situations are schematically depicted in Fig. 2. 

A variational theory which includes all these different contributions was recently proposed and applied for completely stretched polyelectrolyte stars (so-called porcupines ) [203, 204]. As a result, the effective interaction V(r) was very soft, mainly dominated by the entropy of the counterions inside the coronae of the stars supporting on old idea of Pincus [205]. If this pair potential is used as an input in a calculation of a solution of many stars, a freezing transition was found with a variety of different stable crystal lattices including exotic open lattices [206]. The method of effective interactions has the advantage to be generalizable to more complicated complexes which are discussed in this contribution-such as oppositely charged polyelectrolytes and polyelectrolyte-surfactant complexes-but this has still to be worked out in detail. 

Systematic studies on micellar size and structure have been published for poly(styrene-h-acrylic acid) (PS-PAAc) [7, 8], poly(styrene-fr-sodium acrylate) (PS-PAAcNa) [9], or quaternized poly(styrene-h-4-vinyl-pyridine) (PS-P4VPMeI) [10, 11]. It was concluded that the polyelectrolyte chains in the micellar corona are almost fully stretched [8]. The effect of salt concentration was investigated by Guenoun et al. on poly(f-butylstyrene-fr-sodium styrene sulfonate) (PtBS-PSSNa) who observed a weak decrease of micellar size and aggregation number when the salt concentration was increased beyond 0.01 mol/1 [12]. Using small-angle neutron scattering (SANS), the authors could provide additional support for the rod-like conformation of the polyelectrolyte chains in the micellar corona [13]. 

Transmission Electron Microscopy (TEM) has been used to characterize aluminum thin films thermally evaporated (vacuum around 10 4 Torr) on Polyethyleneterephtalate (Mylar) and to correlate the crystallographic structure of the system Al/Mylar and the adhesion of the aluminum films. The adhesion of these films has been measured by a Peel test technique. For the polymer, an amorphous layer (t=12 nm) followed by a crystalline film have been observed on a Corona treated film and the opposite configuration has been found on a bi-axially stretched film. Some spherical precipitation ana interdiffusion zones have also be observed in the Mylar for the films which have the lower coefficient of adhesion (100 g/inch). The main conclusion is the augmentation of the adhesion of the aluminum film as the size of the grains decreases and/or as the microroughness of the Al/Mylar interface increases. 

Metal thin films deposited on polymers are widely used in various industrial domains such as microelectronics (capacitors), magnetic recording, packaging, etc. Despite much attention that has been paid in the recent literature on the adhesive properties of metals films on polyimide (PI)( 1 - 5 ) and polyethyleneterephtalate (PET)((L) it appears that a better knowledge of the metal/polymer interface is needed. In this paper we focus ourself on the relationship between the adhesion and the structural properties of the aluminum films evaporated (or sputtered) on commercial bi-axially stretched PET (Du Pont de Nemours (Luxembourg) S.A.). A variety of treatment (corona, fluorine,etc.) have been applied in order to improve the adhesion of the metallic layer to the polymer. The crystallographic... 

Figure 3 "Semi crystalline" skin for the bi-axially stretched film and "Amorphous skin for the corona treated film.(marked is 12.5 nm)...

The main results obtained for the growth kinetics, the adhesion, and the structure and morpholy of aluminum thin films deposited on bi-axially stretched PET films are the following. (l)For a set of experimental conditions (flux, temperature, and polymer surface), the aluminum film is discontinuous up to 10 nm (island formation) and then become continue. The grain size always increases with the thickness of the aluminum Elm as opposeted to the adhesion which remains rather constant. (2)When the aluminum film is continuous and for one thickness of deposition, the adhesion coefficient increases when the grain size decreases. (3)We found an increase of the adhesion coefficient when the skin of the polymer is "semi-crystalline and when the polymer is pretreated with a corona discharge. (4)The best results (for the adhesion of Al/PET) are found for a polymer treated in a fluorine atmosphere and when the deposition of the aluminum on polymer is done by sputtering. 

The use of selective solvents leads to micelle formation in solution. In toluene PS-fc-P2VP forms micelles with P2VP cores and stretched PS coronas. By means of different techniques it was shown that on polar substrates a two-step adsorption process takes place. In solution single chains adsorb and form a brush. Subsequently this brush collapses upon sample withdrawal from the solution and whole micelles adsorb onto it. These laterally highly ordered patterns are not thermodynamically stable since they are obtained by rapid solvent evaporation. 

Beyond the overlap concentration threshold, c>c = pN/lP, star polymers form a semidilute solution. Because of the fact that the arms in a star are stretched, the scaling theory [24] predicts that the properties of semidilute solutions of star polymers are distinctively different from those of linear polymers. When the polymer concentration c > c, a semidilute solution is envisioned as a system of closely packed and virtually non-interpenetrating (segregated) polymer stars. A further increase in polymer concentration leads to a progressive contraction of the coronae of the individual stars. This contraction results in an increase in the conformational entropy of the partially stretched star arms. 

Alternatively, implementing (40) and (41) leads to a quite different picture for the star structure. Here, the elastic tension in the arms is determined by the local monomer-monomer repulsion only at the edge of the corona, r = I . At r < 7 the arms are stretched more strongly, due to an excess pulling force exerted by the terminal parts of the arms. Therefore, the polymer density profile Cp r,N,R) and the chemical potential A(A,7 ) depend explicitly on N (or the star size R) [123]. 

The conformational characteristics of the corona-forming blocks are controlled by the balance between repulsive monomer-monomer interactions and the conformational entropy penalty for chain stretching. 

At this stage, we neglect the radial gradients in the polymer density distribution within the corona and in the elastic stretching of the A and B chains. In other words, we implement a boxlike model wherein the average concentration of monomer units inside the corona is given by ... 

---