The
effect of molecular properties on the rheological and fatigue
behaviors of solid polystyrene (PS)/polyisoprene (PI) block copolymers
was investigated. Linear model systems of PS–PI (SI), PS–PI–PS
(SIS), and PI–PS–PI (ISI) block copolymers were synthesized
via anionic polymerization with well-defined molecular structure variation
such as block order, PI content, molecular weight, microstructure,
and polydispersity. The different block sequences (SI vs SIS vs ISI)
result, for similar PI contents, in different microdomain sizes, which
correlate with the phase-separated morphologies as quantified via
small-angle X-ray scattering (SAXS). The samples were mechanically
characterized in the solid state via strain sweep tests to obtain
their storage G′(γ0) and
loss G″(γ0) moduli at room
temperature as well as their nonlinear properties determined via the
Fourier transform (FT) of the stress response. The fatigue behavior
was determined via strain-controlled oscillatory torsion tests. First,
the effect of strain amplitude on the number of cycles to failure
was analyzed via Wöhler curves, specifically strain amplitude
vs fatigue lifetime. A significant effect of the block sequence order,
the microdomain size, and the chain dynamics on fatigue resistance
was found. The fatigue resistance of SI diblock with 30 mol % PI outperforms
the SIS or ISI triblock copolymer with a similar composition and,
compared to neat PS, increases by a factor of 10 and even 4500, respectively.
Second, the time-dependent stress response was analyzed via Fourier
transform rheology to better quantify the time-dependent behavior
of the nonlinear mechanical parameters and to determine quantitative
parameters related to failure onset. Since the fatigue tests were
performed under large amplitude oscillatory shear (LAOS), higher harmonics
were detected and the time evolution was quantified in the FT spectra.
Linear parameters such as the storage (G′)
and loss (G″) moduli, as well as the third
(I
3) harmonic over the fundamental one
(I
1), were analyzed, leading to clear
indications related to both brittle or ductile failure mechanisms.