The majority of synthetic polymer gels are formed by the covalent cross-lin
king of linear or branched macromolecules using multi-functional cross-link
ing agents. Such gels are networks, or true macromolecules with (nominally)
infinite molecular weight and consequently they swell rather than dissolve
if immersed in a good solvent. However, there are also a whole class of ma
terials called physical gels where non-covalent crosslinks occur. These sho
w similarities to covalent networks, but because the cross-links are not pe
rmanent, they will show creep behaviour at very long times. Some of these f
orm on cooling a heated solution, such as gelatin gels, while others form o
nly on heating. Also, some gels are thermoreversible, while others are not.
Physical gels can be formed from synthetic or biopolymers. In the latter ca
se non-covalent cross-links often comprise more specific and complex mechan
isms involving, rather than point-like cross-links, "junction zones" of kno
wn, ordered secondary structure such as multiple helices. Typically there i
s a specific, and often intricate, hierarchy of arrangements, which are mor
e Familiar to molecular biologists than to polymer physical chemists. In th
is paper we introduce viscoelastic techniques for characteristing physical
gels, and then relate the properties to the underlying structure at the mac
romolecular and junction zone level. The parallels between synthetic and bi
opolymer gels will also be illustrated. Finally we describe recent work on
the heat-set gelation of globular proteins, and an attempt to relate the im
portant parameter of the gelation time, t(c). to both polymer concentration
and temperature.