The progress made in the understanding of the crystal polymorphism and
morphology of isotactic and syndiotactic poly(propylene) (iPP and sPP
) is reviewed. In 1960, the crystal structure of the stable form of IP
P, the alpha phase, was already solved and the general principles of p
olyolefin chain conformation and crystallography established. The mole
cular analysis of the lamellar branching of alpha iPP-a case of homoep
itaxy specific to this polymer and this crystal form-was given in 1986
. The gamma phase of iPP, solved in 1989, is the first and so far uniq
ue example of a polymer structure with non-parallel chain stems. The b
eta phase is the first example of a frustrated structure in polymers,
and rests on packing of isochiral helices in the unit-cell. The stable
, high temperature form of sPP described in 1988 is based on full anti
chiral packing of helices, whereas the original structure corresponds
to another limiting (but not experimentally observed in pure form) cas
e based on packing of isochiral helices. Details of the molecular stru
cture of IPP and sPP, such as the hand of individual helical stems and
setting of chains, are accessible by crystallographic considerations
which make use of molecular markers provided by the alpha-alpha and al
pha-gamma epitaxies in iPP or by direct visualization by atomic force
microscopy. Copyright (C) 1996 Elsevier Science Ltd.