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A solid can locally exceed its solidus because a thin solute-diffusion layer changes composition faster than thermal conduction changes temperature. Near a melting phase boundary, a depleted solid can join the equilibrium solidus at the interface while the adjacent, more concentrated solid remains above its own lower solidus. The assumed single sharp interface is then thermodynamically unstable to additional melting and may be replaced by a mushy layer.

Use $\ell =L/c_p$, $ϵ=\sqrt{D_s/D_l}$ and $\delta =\sqrt{D_l/\kappa }$, with $0<k_D<1$. Equal reference densities and constant material properties are implicit in these diffusion balances. Put $a(t)=2\lambda \sqrt{D_{l}t}$ and $T_a=-m{C}_a$. The four similarity fields areHere the same letters $T_s,T_l,C_s$ on the right denote their far-field values. Substitution into the heat and solute diffusion equations verifies the fields; their interface values and far-field limits verify every boundary condition. The concentration has an equilibrium jump from $k_D{C}_a$ to $C_a$, whereas temperature is continuous.

The interfacial conservation laws areFor example,Since $\dot{a}=\lambda \sqrt{D_l/t}$, dividing the two jump conditions by $\dot{a}$ gives, for nonzero $\lambda$,where $F(z)=\sqrt{\pi }z{e}^{z^2}\mathrm{erfc}z$. At $\lambda =0$, use the undivided flux conditions or the continuous limit, rather than divide by zero. The liquidus relation and the segregation coefficient also give the solidus $T_S(C)=-mC/k_D$.

For the thermal expansion, write $z=\delta \lambda$ and useKeeping the constant terms in these reciprocals is essential for the full first-order answer. The result isThe remainder has this form for bounded $\lambda$; a looser $O({\delta }^2)$ statement is also valid in the distinguished scaling $\ell =O({\delta }^{-1})$. Dropping the temperature-difference term while claiming first-order accuracy for fixed $\ell$ would be incorrect.

Solving the solute balance algebraically givesFor fixed positive $\lambda$, $F(-\lambda /ϵ)\to -\infty$, and $C_a\to 0$, with a positive exponentially small correction. For fixed negative $\lambda$, $F(-\lambda /ϵ)\to 1$, andIt falls from $C_s$ as $\lambda \to -\infty$ to zero as $\lambda \to 0^{-}$. The outer positive branch is zero. For finite $ϵ$ the transition is rounded over $|\lambda |=O(ϵ)$; the exact zero-speed limit is $C_a(0)=ϵC_s/(1+k_Dϵ)$, not an actual concentration discontinuity.

To count speeds, take the leading distinguished thermal balance, set $\Sigma =T_l+T_s$ and $K=\sqrt{\pi }\delta \ell$, and combine $T_a=-m{C}_a$ with the thermal result:This is the intended leading approximation when $\delta \ell =O(m{C}_s)$ and $T_l-T_s=O(1)$. The full first-order expression instead replaces $K$ by $\sqrt{\pi }\delta [\ell +2(T_l-T_s)/\pi ]$. Thus the printed threshold is asymptotic, not an exact criterion for finite $\delta ,ϵ$.

For $r=-\lambda >0$, put $H(r)=\sqrt{\pi }r{e}^{r^2}\mathrm{erfc}(-r)$. The small-solid-diffusivity melting concentration is $C_{s}H/(1+H)$, soThe second term decreases strictly from $2m{C}_s\sqrt{\pi }$ to zero. One can check the strict decrease without guessing its shape. Set $A(r)=\sqrt{\pi }{e}^{r^2}\mathrm{erfc}(-r)$, so $A^{\prime }=2rA+2$, $A\ge \sqrt{\pi }+2r$, and $H=rA$. Direct differentiation givesThe bracket increases with $A$ on $r\ge 0$. Substituting its lower bound yields a polynomial with constant coefficient $\pi -2>0$ and all other coefficients positive. Hence $[H^{\prime }/(1+H{)}^2{]}^{\prime }<0$, as claimed.

If $\delta \ell >2m{C}_s$, then $K>2m{C}_s\sqrt{\pi }$ and $\Sigma (r)$ increases from zero to infinity. The freezing branch has $\Sigma =-K\lambda <0$ and is also monotone. Together these give one speed for each imposed sum within the approximation. If $0<\delta \ell <2m{C}_s$, the melting branch initially decreases, has exactly one minimum and then increases to infinity. For sums between that minimum and zero there are two melting speeds plus one freezing speed: three solutions. At the lower fold there are two distinct speeds, one being a double solution. At zero the limiting outer branches join; finite solid diffusivity rounds the join into a nearby fold. Away from the fold values the other sums have one solution. At the threshold itself the initial slope vanishes; it is the transition between these cases.

For $\Sigma >0$, the solution is on the melting branch $\lambda <0$. Its thermal layers have scale $\sqrt{\kappa t}=\sqrt{D_{l}t}/\delta$, much larger than the liquid-solute scale $\sqrt{D_{l}t}$. Because the front is retreating, the solid solute layer is thinner still:This follows by expanding the large-positive-argument complementary error function ratio on the solid side: near $a$, its decay length is $D_s/|\dot{a}|$. Using simply $\sqrt{D_{s}t}$ would miss the retreating-front compression of that layer.

Across this narrow layer, solid concentration drops from almost $C_s$ to $k_D{C}_a$, while temperature stays almost $T_a$. At the interface $T_a=T_S(k_D{C}_a)$. Moving slightly into the solid increases its concentration toward $C_s$, lowering its solidus to $-m{C}_s/k_D$, whereas the temperature has barely changed. Since $C_a<C_s$ and $k_D<1$, $T_a=-m{C}_a>-m{C}_s/k_D$. Thus an adjacent region can satisfy $T>T_S(C)$: constitutional superheating. Its existence is especially clear when far-field solid is initially stable but heat diffuses across the narrow composition layer.

The phase-diagram path goes from $(C_s,T_s)$ through a broad thermal rise, then nearly horizontally toward $(k_D{C}_a,T_a)$ across the thin solid diffusion layer. At the interface it traverses the isothermal equilibrium tie line to $(C_a,T_a)$. On the liquid side concentration falls to zero over the liquid-solute layer, while the remaining thermal adjustment to $T_l$ takes place over the much wider heat layer. The path of the depleted solid approaches the solidus from its superheated side. That region should melt at additional sites or develop a two-phase mushy layer; the original single-boundary similarity construction is then a mathematical branch rather than a physically stable description of the entire sample.