Polystyrene annealing

Two experimental techniques are employed to investigate the dynamic glass transition for thin polystyrene annealed at least 12 hours at 150°C in an oil-free... 

FIGURE 4.7 Results for MTDSC experiments on polystyrene annealed for different lengths of time up to 45 min. The inset bars are a guide to the scale for each signal. 

Fig. 2.20 Examples of electron micrographs of polymers, (a) A defocussed bright-field image of a thin film of isotactic polystyrene annealed and crystallised at about 170 °C (b) An image of a fracture surface replica from a sample of linear polyethylene crystallised from the melt at 4.95 kbar. ((a) Adapted by permission of Masaki Tsuji and (b) adapted from Principles of Polymer Morphology by D. C. Bassett. Cambridge University Press 1981.)...

Roe, R. J., and Curro, J. J., Small angle x-ray scattering smdy of density fluctuation in polystyrene annealed below the glass transition temperature. Macromolecules, 16, 428-434 (1983). 

Figure 1.10. Typical results for a glass transition with different degrees of annealing (polystyrene annealed at 90°C and re-heated at 2°C/niin, period 40 s, amplitude 0.2FC...

Figure 3.10. ACp versus annealing temperature for polystyrene. Annealing time was 1 h.

In numerous applications of polymeric materials multilayers of films are used. This practice is found in microelectronic, aeronautical, and biomedical applications to name a few. Developing good adhesion between these layers requires interdiffusion of the molecules at the interfaces between the layers over size scales comparable to the molecular diameter (tens of nm). In addition, these interfaces are buried within the specimen. Aside from this practical aspect, interdififlision over short distances holds the key for critically evaluating current theories of polymer difllision. Theories of polymer interdiffusion predict specific shapes for the concentration profile of segments across the interface as a function of time. Interdiffiision studies on bilayered specimen comprised of a layer of polystyrene (PS) on a layer of perdeuterated (PS) d-PS, can be used as a model system that will capture the fundamental physics of the problem. Initially, the bilayer will have a sharp interface, which upon annealing will broaden with time. 

Polymer-polymer fractal interfaces may result from the interdiffusion of monomers or of polymers themselves. Koizumi et al. [31] annealed the interface between polystyrene and a styrene-isoprene diblock polymer at 150 C and showed extensive roughening of the interface by mutual interdiffusion on a micron scale (Fig. 8). 

Fig. 8. Electron micrograph.s showing the interface between polystyrene (top) and a styrene-isoprene diblock polymer (bottom), annealed at I50°C for the times shown. Isoprene units are stained and appear black) (reproduced from [31], copyright American Chemical Society).

Fig. 10. X-ray reflectivity curves of polystyrene (PS)/poly-p-bromostyrene (PBrS) on a glass substrate before (solid line) and after annealing for 13 h at 130 °C (dashed tine) [191]. The width of the interface changes from 1.3 nm to 2.0 nm due to interfacial mixing of components. The X-ray wavelength is 0.154 nm and films have a thickness of 37.8 nm (PS) and 45.0 nm (PBrS), respectively...

Zink et al. used a blend of polystyrene (hPS) and its deuterated counterpart (dPS), both of molecular weight 1.95 x 106 (abbreviated 1.95 M). The average volume fraction (4>dPS) of deuterated polystyrene was 30%. The polymers were dissolved in toluene and spin cast on thin silicon wafers (about 10 x 10 mm), the resulting film thickness being about 300 nm. The samples were annealed at 245°C for 8 days, and the measurement of the resulting depth profiles was conducted by NRA using a monoenergetic 700 keV 3He beam. The nuclear reaction employed can be written ... 

Figure 2. Time dependence for 600K MW polystyrene films spin cast at 8,000 rpm and annealed at different temperatures.

For the distyrylbenzene carbon-centered tetramer 46b, the fluorescence spectrum in the solid him differs from the spectra in solution or in a polymer matrix due to excimer formation [93]. A concentration of 5% in a polystyrene matrix is sufficient for a distinct broadening of the emission. For the higher homologue 46c, a fluorescence maximum of 472 nm was measured in freshly prepared films. If the film is thermally annealed, the spectrum shifts to 511 nm, probably due to intermolecular arrangement that favors excimer formation. 

The major features for advanced photo-systems relative to the base film are a small-size thrust cartridge and return inside the cartridge. These features require low core-set curl values and high mechanical strength. The cellulose triacetate (CTA), polycarbonate and PET materials currently used in the photographic industry are not able to satisfy these requirements. Some newly developed film materials, such as modified-PET and syndiotactic polystyrene, were also unable to satisfy such requirements. It is known that annealing films just below the Tg (BTA treatment) could reduce core-set curl tendencies. BTA treatments of... 

To the best of our knowledge, the supercoil conformation of the monoden-dron jacketed polystyrene is one of the first observations of a defined tertiary structure in synthetic polymers. The plectoneme conformation could be caused by underwinding or overwinding of a backbone from its equilibrium state [168]. Quick evaporation of the solvent certainly can cause a residual torsion in the molecule as it contracted in itself. Unlike macroconformations of biomolecules, where the tertiary structures are often stabilized by specific interactions between side groups, the supercoil of the monodendron jacketed polymers is metastable. Eventually, annealing offered a path for the stress relaxation and allowed the structural defects to heal [86]. 

In a kinetic sense, the system is a better solvent than HFIP alone. We postulate that MeCl2 swells the amorphous regions of PET thereby providing HFIP with an easy access to the crystalline regions. This swelling action does not occur with HFIP alone, and the dissolution process takes much longer. At room temperature, amorphous PET is Instantaneously solubilized by this solvent system. PET that has been annealed for >24 hr at 220 C to yield maximum crystallinity dissolves in <4 hr at room temperature. PET annealed in this manner does not dissolve in pure HFIP after 14 days at room temperature. Poly(butylene terephthalate) and aliphatic polyamides are soluble in this solvent system. Polystyrene is also soluble, which permits conventional calibration and the use of the universal calibration approach. We have determined the Mark-Houwlnk relationships for PET and polystyrene in 70/30 MeCl2/HFIP to be... 

Monsanto Hi-Flow 77 Polystyrene. The viscosity-average molecular weight found in this work was 284,000. The ratio Mw/Mx reported by the manufacturer is 2.67. The samples were prepared by injection molding in a 1-ounce Mini-Jector molding machine, followed by annealing for 24 hours at 75°C. 

The formation of solid solutions appears from the X-ray diffraction spectrum for a system formed by a 1 1 (weight) mixture of isotactic polystyrene and of a styrene//>-methylstyrene copolymer (30 moles-% / -methylstyrene), obtained after melting followed by a proper annealing treatment (2). The solid solution is possible because the two different... 

A positive Hamaker constant corresponds to an attractive force between the silicon oxide-polystyrene and the polystyrene-air interfaces. This implies that the film is not stable. If it is thin enough and has a chance, for instance when annealing, the film ruptures and holes are formed. 

Fig. 11 Craze in commercial polystyrene showing the characteristic steps nucleation through void formation in a pre-craze zone, growth of the fibrillar structure of the widening craze by drawing-in of new matrix material in the process zone, and final breakdown of the fibrillar matter transforming a craze into a crack (the crack front is more advanced in the center of the specimen, shielded by a curtain of unbroken fibrils marked by the arrow). The fibril thickness depends—of course—on the molecular variables, the strain rate-stress-temperature regime of the crazing sample and on its treatment (preparation, annealing) and geometry (solid, thin film) for PS typical values of between 2.5 and 30 nm are found [1,60,61]...

Figure 6. X-ray diffraction patterns of (a) a crude sample of polystyrene and (b) the ether-insoluble fraction of polystyrene after hot-pressing and annealing (20)...

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