Sample overloading effects in polymer characterization by field‐flow fractionation

There are two subtechniques of field-flow fractionation (FFF), thermal FFF and flow FFF, that have been successfully employed for polymer fractionation and characterization. These techniques are primarily analytical in nature, yielding accurate polymer characteristics from small sample loads (∼ 10 μg or less, depending on detection sensitivity). In this study the effects of increasing sample size are examined. Modest increases in load are found to result in shifts toward higher retention volumes. These modest loads also result in some broadening of the sample peaks without a major loss of peak symmetry. Excessive loading, by contrast, appears to give rise both to skewed peaks and to new artifact peaks at higher levels of retention. These observations are discussed in terms of the concentration dependence of various properties (viscosity, diffusivity, thermal diffusivity) which influence polymer transport through the FFF channel. The results are used to indicate upper limits to suitable sample concentrations.