General Solution to the Band-Broadening Problem in Polymer Molecular Weight Distributions

2005 ◽  
Vol 58 (3) ◽  
pp. 178 ◽  
Author(s):  
Jeffrey V. Castro ◽  
Kim Y. van Berkel ◽  
Gregory T. Russell ◽  
Robert G. Gilbert
Keyword(s):  
Molecular Weight ◽  
Free Radical ◽  
Radical Polymerization ◽  
Free Radical Polymerization ◽  
Size Exclusion ◽  
Full Detail ◽  
Band Broadening ◽  
Molecular Weight Distributions ◽  
Weight Distributions ◽  
Exclusion Chromatography

A method is developed for overcoming the problem of band broadening (where a sample which is monodisperse in molecular weight elutes over a range of elution volumes) in order to obtain accurate molecular weight distributions of polymers using size exclusion chromatography (SEC). It is proved that the SEC signal from an exponential number distribution (as obtained from free-radical polymerization under certain conditions) has the same functional form at the maximum, irrespective of band broadening. This leads to a method for quantifying the band broadening from any SEC trace, and hence for deconvoluting the trace to obtain the true distribution—by free-radical polymerization one should synthesize ‘standards’ which have exponential distributions and then carry out least-squares fitting to find the corresponding broadening function. The new method opens the way for mechanistic understanding and rate parameters to be obtained from the full detail that has hitherto been inaccessible in molecular weight distributions.

Relationships between Molecular Weights and Rheological Properties of Asphalts

1996 ◽  
Vol 1535 (1) ◽  
pp. 10-14 ◽  
Author(s):  
Jan F. B ranthaver ◽  
Raymond E. Robertson ◽  
John J. Duvall
Keyword(s):  
Molecular Weight ◽  
Rheological Properties ◽  
Size Exclusion Chromatography ◽  
Size Exclusion ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Molecular Associations ◽  
Weight Distributions ◽  
Exclusion Chromatography ◽  
Microstructural Model

It is known that the rheological properties of mixtures of organic compounds are functions of molecular weight distributions. However, with respect to asphalts, which are composed of many different compounds and compound types, molecular weights are difficult to measure. This difficulty occurs because the molecular associations that form are held together by forces of varying strengths and are partly broken up by heat and solvents. In theory, the strongest molecular associations in asphalts should have the greatest influence on the rheological properties of asphalts. These associations would be expected to be the major contributors to the asphalt's behaving as if it were a relatively high molecular weight material. Asphalt molecular associations should be isolatable by means of size exclusion chromatography. Several fractions of varying molecular weights (measured by membrane osmometry and vapor phase osmometry) were isolated from Strategic Highway Research Program (SHRP) asphalt AAD-1 by preparative size exclusion chromatography. Molecular weights of these fractions ranged from approximately 2,000 daltons to over 40,000 daltons. When these fractions were independently mixed with asphalt AAD-1 solvent moiety, mixtures were obtained whose rheological properties were a function of the molecular weights and concentrations of the associated materials. These results support the microstructural model of asphalt proposed during SHRP. The results also suggest that the unusual rheological properties of some asphalts may be explained by measuring molecular weight distributions. This type of information may be useful for modification of asphalts to achieve desirable rheological properties.

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