Viscosity of Dilute Solutions of Long Chain Polymer Molecules

1958 ◽  
Vol 28 (1) ◽  
pp. 88-90 ◽  
Author(s):  
H. L. Bhatnagar ◽  
A. B. Biswas ◽  
M. K. Gharpurey
1969 ◽  
Vol 91 (3) ◽  
pp. 371-373 ◽  
Author(s):  
C. W. McCutchen ◽  
J. F. Wilkins

Animal joints are lubricated by two complementary mechanisms. Weeping lubrication carries most of the joint load hydrostatically, leaving only a small fraction of the total to be carried by rubbing of the solid “skeletons” of the two cartilages. This rubbing is, in turn, lubricated by the synovial mucin; i.e., by long chain polymer molecules dissolved in the joint fluid. There is good evidence that the mucin molecules adsorb to the surfaces and provide boundary lubrication. In this paper we examine further this adsorption processs using a bearing whose two surfaces are rubber and glass, respectively. It is found that the lubricating ability of the mucin is good if it is applied to the bearing in a solution with about physiological salt concentration. At higher salt concentrations the lubrication is comparatively poor, while at zero salt concentration it is very bad indeed. If, on the other hand, the mucin is applied at physiological salt concentration, and then the salt and unadsorbed mucin are washed away with distilled water the lubrication remains good, and has, on occasion, even improved. Once the mucin has been adsorbed the entire range of salt concentration can be explored, with the lubrication becoming worse at high salt concentration and then recovering in greater or lesser degree when the salt is washed off. It seems, then, that the salt concentration affects lubrication in two ways. It can upset the adsorption of the lubricating film, and it can change the lubricating effectiveness of the film once it is adsorbed.


Long-chain polymer molecules are approximated by a model consisting of isodimensional segments which tend to arrange themselves in co-linear succession. A fraction f of the bonds is assumed to be ‘bent’ out of the co-linear direction of preceding segments. The fact that the free energy of solution derived using the lattice model separates into (a) a mixing term dependent only on the concentration, and (b) a disorientation term depending on f but not on the concentration, leads to the concept of an equilibrium ‘flexibility’ f which is characteristic of the polymer chain at a given temperature. This f must exceed a specified critical value, which decreases with dilution, if the disordered phase usually considered to occur is to be more stable than an ordered one in which the chains assume their preferred rod-like form and lie parallel to one another. Transition between the two states should be co-operative, and should involve a latent heat (owing to the change in intramolecular configurational energy) even in the absence of a change in the intermolecular energy. The concept of a phase transition due solely to intramolecular forces thus arises. Configurational dimensions of various polymers are such as to suggest that inflexibility may be a dominant factor in causing them to crystallize. This is certainly true for cellulose derivatives, probably also for polytetrafluoroethylene, and possible for polymethylene as well. Intramolecular forces favouring the rod-like form are, doubtless of major importance also in bringing about crystallization of proteins in the α-form.


Author(s):  
Shitanshu Devrani ◽  
Rahul Kumar Tiwari ◽  
Rajat Sharma ◽  
Mathur P. Rajesh ◽  
Ashish Kapoor

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