Polymer blends light scattering

Light scattering of polymer blends also helps in characterizing the different phases of PBAs. 

Detection is also frequently a key issue in polymer analysis, so much so that a section below is devoted to detectors. Only two detectors, the ultra-violet-visible spectrophotometer (UV-VIS) and the differential refractive index (DRI), are commonly in use as concentration-sensitive detectors in GPC. Many of the common polymer solvents absorb in the UV, so UV detection is the exception rather than the rule. Refractive index detectors have improved markedly in the last decade, but the limit of detection remains a common problem. Also, it is quite common that one component may have a positive RI response, while a second has a zero or negative response. This can be particularly problematic in co-polymer analysis. Although such problems can often be solved by changing or blending solvents, a third detector, the evaporative light-scattering detector, has found some favor. 

Due to light scattering, crystalline polymers mostly yield turbid films.Their blends with other polymers are always demixed because polymers are not able to form mixed crystals. Consequently, crystallizable polymers only yield homogeneous blends above their melting point. As soon as crystallization sets in, the components will separate. 

The first data on polymer systems were collected via (laser-) light-scattering techniques [1] and turbidity measurements, further developed by Derham et al. [2,3]. Techniques based on the glass-transition of the polymer-blend constituents were also tested, such as DSC, Dynamic Mechanical Spectroscopy, and Dielectric relaxation [4]. Films made from solutions of... 

We developed an experimental procedure that can be applied to highly viscous polymer blends. In the DSM micro-extruder [6], polymers are blended in the melt, at the desired temperature and pressure, and injected into a small capillary tube which is immediately sealed with a floating plug. This capillary cell is placed in a small window autoclave and a laser beam enters the capillary cell at the lens-shaped bottom end. The intensity of the light scattered by the polymer system is recorded at two scattering angles (as a function of pressure and temperature). 

EOS models were derived for polymer blends that gave the first evidence of the severe pressure - dependence of the phase behaviour of such blends [41,42], First, experimental data under pressure were presented for the mixture of poly(ethyl acetate) and polyfvinylidene fluoride) [9], and later for in several other systems [27,43,44,45], However, the direction of the shift in cloud-point temperature with pressure proved to be system-dependent. In addition, the phase behaviour of mixtures containing random copolymers strongly depends on the exact chemical composition of both copolymers. In the production of reactor blends or copolymers a small variation of the reactor feed or process variables, such as temperature and pressure, may lead to demixing of the copolymer solution (or the blend) in the reactor. Fig. 9.7-1 shows some data collected in a laser-light-scattering autoclave on the blend PMMA/SAN [46],... 

Compared to binary mixtures of low molecular fluids, the critical behavior of polymer blends has been much less explored so far. However, a number of interesting static and dynamic critical phenomena in polymer blends attract increasing attention [4, 5], Neutron, X-ray, and static light scattering experiments belong to the major techniques for characterizing the static properties of polymer blends. Photon correlation spectroscopy (PCS) has traditionally been the method of choice for the investigation of the dynamics of critical [6-9] and noncritical [10-12] polymer blends. 

The above discussion deals with the base polymer only. One can see that if the additive system imparts light scattering similar to these examples above, the effect on coloring the total resin system can be dramatic. We begin our discussion of additives by looking at polymer blends, where the secondary polymer can be considered an additive to the continuous base polymer. 

One can assume that blends of polymers will be more difficult to color than any single component by itself. Diffuse reflection can increase due to internal light reflection or scattering at phase interfaces if the polymers are at least partially immiscible or their refractive indices are significantly different. Blends of translucent polymers are typically more opaque than either resin alone. Furthermore, colorant stability (thermal or chemical) can be adversely affected by the presence of the other polymer(s). As in the case of neat polymers, both circumstances will result in a restricted achievable color gamut for the polymer blend. An example of a prominent polymer blend is GE s Noryl (PS/PPO), which certainly colors much differently than the polystyrene component by itself. 

In flow the challenge has been to write convincing equations that couple concentration and composition gradients to elastic stresses and the bulk flow field. When done within a two-fluid model for polymer solutions transitions in light-scattering patterns seen in experiment may be explained. Extensions to polymer blends are potential candidates as explanations of shear-induced shifts of the spinodal and biphasic islands seen experimentally. - ... 

Polymer conformations are studied by various scattering experiments (light, small-angle X-ray and neutron scattering). These techniques are based on the contrast between the polymer and the surrounding media (solvent in the case of polymer solutions and other polymers in the case of polymer melts or blends). The contrast in light scattering arises from differences in refractive index between polymer and solvent, and the scattered intensity is proportional to the square of the refractive index increment dn/dc [see Eq. (1.86)]. 

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