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Use polymer volume fraction $\varphi$ horizontally and the Flory interaction parameter $\chi$ vertically. Lower $\chi$ gives better solvent quality. The simplest Flory–Huggins solution theory assigns the dimensionless mixing free energy per lattice siteThus $\chi <1/2$ gives positive excluded volume and a good-solvent coil, $\chi =1/2$ is the long-chain theta condition, and $\chi >1/2$ is the poor-solvent side. It is the net two-segment interaction that vanishes at theta, not every molecular force.

At fixed good-solvent quality, the polymer overlap volume fraction ${\varphi }^{\ast }\sim N{a}^3/R_g^3$ separates isolated coils from a semidilute polymer solution. Above overlap, many chains interpenetrate, but there is still solvent on the segment scale. As $\varphi$ approaches order unity the solution is concentrated; these concentration-regime boundaries are crossovers, not first-order phase transitions. The overlap fraction increases from order $N^{-4/5}$ in a strong good solvent toward order $N^{-1/2}$ at theta. The crossover can be expressed as ${\varphi }^{\ast }\sim N^{-4/5}(1-2\chi {)}^{-3/5}$ while $1-2\chi \gg N^{-1/2}$; it saturates at the theta scaling when that condition fails.

On the poor-solvent side there can instead be coexistence of polymer-poor and polymer-rich phases. The binodal follows a common tangent of $f$; the spinodal followsThe critical point of a Flory–Huggins polymer solution isFor finite $N$, ${\chi }_c$ lies above $1/2$. Therefore poor solvent does not automatically mean demixing at every concentration, and an overlap line must not be mistaken for a coexistence boundary. The original figure uses the stated ideal model for an illustrative chain length; it does not assert a measured phase boundary. A vertical temperature axis would additionally require a material-specific relation $\chi (T)$.

Overlap means roughly one coil per coil volume. With segment volume $a^3$, the corresponding polymer overlap volume fraction isFor a strong good solvent, $R_g\sim a{N}^{3/5}$, and henceor about 0.063% by volume in the unit-prefactor scaling convention. The segment length cancels. A coil has no sharply defined boundary, so using $4\pi R_g^3/3$ or retaining a size amplitude changes an order-one prefactor. This calculation is a scaling estimate, not an exact volume-fraction measurement.

The polymer overlap volume fraction counts the segment volume of one chain divided by its coil volume. If the segment volume is $v_0$ and $R\sim b{N}^{\nu }$, then ${\varphi }^{\ast }\sim (v_0/b^3)N^{1-3\nu }$. The site-volume convention $v_0\sim b^3$ gives $N^{-4/5}$ for the three-dimensional Flory approximation and $N^{-1/2}$ for an ideal chain. A geometric coil volume such as $4\pi R_g^3/3$ changes a prefactor; segment length and segment volume are not generally interchangeable without a model convention.