Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2023 / Paper 2 / Section A(iii) / 18

The Flory interaction parameter $\chi$ measures the free-energy penalty of unlike block contacts relative to like contacts, in units of $k_{B}T$. The degree of polymerization $N$ counts the reference segments per chain, using the segment-volume convention associated with $\chi$. Their product, the block copolymer segregation strength $\chi N$, compares the tendency to avoid unlike contacts with the entropy cost of organizing and stretching connected chains.

At small $\chi N$, the diblock copolymer is disordered. Increasing $\chi N$ can cause microphase separation: the blocks form distinct domains, but their covalent connection prevents complete macroscopic separation. Domain interfaces cost energy while chain stretching and lost configurations cost entropy; their competition selects a finite domain scale.

A common temperature law is $\chi =A/T+B$, so increasing temperature often decreases segregation when $A>0$. This is not a universal sign law for every polymer pair. For an intact, fixed chain, $N$ does not change just because temperature or solvent concentration changes.

Adding a nonselective good solvent usually dilutes unlike-block contacts and reduces an effective segregation strength; it does not chemically shorten the chain. A selective solvent additionally changes domain swelling and solvent-block interactions. One needs a ternary-mixture description, or a clearly defined effective $\chi$, rather than treating the melt's $\chi$ as a universal solvent-concentration function.^[ref]

For the dry diblock copolymer, the block volume fractionis the volume assigned to the polyisoprene block divided by total polymer volume, not its mass fraction or the volume fraction of polymer in the whole solution. It controls domain curvature and topology. Similar block volumes favor alternating lamellae; a smaller minority block generally favors curved interfaces, cylinders and eventually isolated spherical domains.

The chemical block lengths are fixed. Temperature changes their volumes only through thermal expansion, so $f_{PI}$ is often approximated as temperature independent; unequal expansion coefficients can produce a small change.

Solvent requires a distinction between dry composition and swollen domain composition. The dry $f_{PI}$ remains fixed. If solvent volumes $V_{s,PI}$ and $V_{s,PS}$ partition into the two domains, an effective swollen fraction isA polystyrene-selective solvent therefore lowers $f_{PI}^{\mathrm{eff}}$, whereas a polyisoprene-selective solvent raises it. Equal proportional swelling leaves this effective ratio unchanged.

Reading the lowest point of the order-disorder boundary in the supplied experimental diagram gives approximately(about $0.45$–$0.47$, allowing for the graphical resolution). The ordered region just above that minimum is lamellar.

This is a reading of the supplied polyisoprene-polystyrene phase diagram. It should not be replaced by the often quoted symmetric-chain mean-field theory value $10.5$: that refers to a different idealization and is not the minimum drawn here.

The starting point is in the lamellar region. Preferential swelling of polystyrene makes polyisoprene the increasingly small minority domain, so the relevant effective composition moves left from $f_{PI}^{\mathrm{eff}}=0.45$.

If segregation stayed near $\chi N=35$, following the horizontal path in the supplied diagram would give lamellae → hexagonally perforated layers → hexagonally arranged PI cylinders → PI spheres, before sufficient asymmetry reaches the disordered region. The perforated-layer interval is narrow, around $f_{PI}\simeq 0.36$–$0.40$ at this segregation strength; precise boundaries should not be read more accurately than the figure allows.

Solvent also changes effective segregation, so the actual trajectory need not be horizontal. If it passes closer to the order-disorder boundary, it can enter the narrow double gyroid region instead of, or after, the hexagonally perforated layer phase. Greater dilution can cause disorder before all the ordered morphologies appear. Thus a plausible alternative is lamellae → gyroid → cylinders → disorder.

The robust prediction is the change toward minority-PI curved structures, not a guarantee that every named phase occurs. A solvent partition coefficient and a concentration-dependent interaction model would be needed to locate the actual path quantitatively; applying a dry-melt diagram to a swollen material is an effective approximation.