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The invariant liquid-plus-two-solids equilibrium of a binary eutectic system at fixed pressure. It specifies both the eutectic temperature and the eutectic composition.

The transformation $L\to \alpha +\beta$ in which one liquid produces two solid phases at a binary eutectic composition and temperature under fixed pressure. The resulting two-phase constituent must be distinguished from either individual thermodynamic phase.

For pure solid rejecting all solute, pulling speed $V>0$, solutal diffusivity $D$ and finite solute inventory per unit area $N$, a stationary planar front has $C(z)=C_I{e}^{-Vz/D}$ in its liquid half-space. The advection-diffusion equation gives this profile, and ${\int }_0^{\infty }Cdz=N$ fixes $C_I=VN/D$. A liquidus $T_I=-m{C}_I$ fixes its position in an imposed temperature gradient. The pure-solid branch requires $C_I<C_E$, where $C_E$ is the eutectic composition.

Eutectic solidification is the coupled transformation of a liquid into two distinct solid phases at the eutectic temperature and composition, $L\to \alpha +\beta$. At fixed pressure in a binary system the three-phase equilibrium is invariant. An exactly eutectic liquid can therefore finish freezing at one temperature, instead of over a broad liquid-plus-solid interval.

Eutectic compositions are useful in joining alloys, for example silver-copper brazing filler: the comparatively low melting temperature and narrow freezing interval help liquid flow into a joint and then solidify. Alternating growth of the two phases often produces a fine lamellar eutectic microstructure. The eutectic is a two-phase aggregate, not a new single solid phase.

The cooling curve first falls in the entirely liquid field. On crossing the liquidus, primary Ag-rich $\alpha$ begins to grow. Latent heat release makes the descent shallower; the remaining liquid becomes richer in copper and approaches the eutectic composition.

At $779^{\circ }\mathrm{C}$, the remaining liquid solidifies as $\alpha +\beta$, giving an isothermal arrest under the ideal equilibrium, heat-extraction model. After the liquid is exhausted, temperature falls through the two-solid field. Continued loss of solid solubility causes additional redistribution and precipitation; it does not require another invariant liquid-freezing plateau.

Immediately before the eutectic reaction, the remaining liquid fraction isThe arrest represents freezing of roughly $58\%$ of the sample by mass. Its duration cannot be calculated without the heat-extraction rate and latent heat, and the onset temperature cannot be calculated exactly from the supplied phase-diagram points alone.

Take $z$ upward from the unperturbed interface in the apparatus frame, with liquid at $z>0$ and pulling velocity $-V{\mathbf{e}}_z$. The primary ice contains no salt. We use the dilute, equal-density approximation and neglect fluid motion relative to the mould. The initial salt inventory per unit horizontal area, with a common density factor suppressed, is $N=h{C}_0$. Its conservation is essential: the far liquid has zero concentration, so an imposed nonzero far-field composition would describe a different experiment.

The steady advection-diffusion equation is $-V{C}^{\prime }=D{C}^{\prime \prime }$. Decay into the pure water and interfacial salt rejection giveSince ${\int }_0^{\infty }C(z)dz=D{C}_I/V=N$, the finite-inventory directional salt rejection solution isThe decay length is $D/V$. Local liquidus equilibrium givesThus the thermal apparatus selects the interface position at this isotherm. The stated speed inequality is precisely $C_I<C_E$, so the interface is warmer than the eutectic temperature, $T_I>T_E=-m{C}_E$. These are steady values after the initial finite saline layer has rearranged; the final exponential distribution is not confined to the original depth $h$.

For $Vh{C}_0/D>C_E$, a steady pure-ice front would require an interfacial composition beyond the eutectic composition. That branch is unavailable. During the transient, rejected brine concentrates until it reaches $C_E$; secondary salt-bearing crystals can then form and the residual brine freezes as an eutectic system. Salt is incorporated into the product rather than remaining indefinitely in a super-eutectic exponential layer. The detailed pattern can include brine pockets and a nonplanar freezing region; it depends on the thermal history and the morphological stability. The speed inequality alone does not decide that latter stability.

For the stability calculation use an interface displacement $\eta =\hat{\eta }{e}^{ikx+st}$ and a liquid perturbation $c=\hat{c}{e}^{ikx+st-qz}$. Here $k>0$ is the wavenumber, $s$ is the temporal rate and $\Re q>0$ gives spatial decay. The frozen thermal field is $T_I+Gz$. Define $\Gamma ={\gamma }_{sl}{T}_m/(\rho L)>0$, where ${\gamma }_{sl}$ is solid-liquid surface energy, $T_m$ is absolute pure-solvent melting temperature, $\rho$ is mass density and $L$ is specific latent heat. For a solid protrusion into liquid the curvature is $\mathcal{K}=-{\eta }_{xx}=k^2\eta$, and the Gibbs-Thomson effect gives local equilibrium $T=-mC-\Gamma \mathcal{K}$. We assume isotropic surface energy and instantaneous interface kinetics, so no kinetic undercooling term is present.

Linearizing the equilibrium condition at the displaced interface givesThe perturbation advection-diffusion equation givesThe local solute balance at a moving graph, to first order, isIts perturbation is $(V-Dq)\hat{c}+s{C}_I\hat{\eta }=0$, because the terms $D\eta C^{\prime \prime }(0)$ and $V\eta C^{\prime }(0)$ cancel. Consequently the full frozen-temperature solutal interface dispersion isNo quasistatic approximation to solute diffusion was made here. For a growing mode the unique admissible liquid root isWriting $b=(G+\Gamma k^2)/(m{C}_I)$ and eliminating $s$ gives $(q-V/D)(q-V/D+b)=k^2$. The root continuously connected to the growing interface branch is thereforeIn particular, unstable wavelengths exist exactly when $mV{C}_I/D>G$, and their band isThis is the constitutional supercooling criterion: immediately above the plane, the local liquidus rises at rate $-m{C}^{\prime }(0)=mV{C}_I/D$, so it overtakes the imposed thermal gradient when that rate exceeds $G$. The Gibbs-Thomson effect cuts off short waves. At long wavelength $s\sim D(V/D-b)k^2/b$ for positive $G$. The exactly uniform inventory-changing displacement is not an instability of a fixed-inventory experiment. On stable branches the full diffusion problem also admits relaxation transients; the root selection above is sufficient to identify every exponentially growing interface mode.

If one additionally neglects the perturbation time derivative in the liquid diffusion equation, the alternative reduced rate isIt has the same onset and cutoff, but need not have the same rate away from the slow-growth regime. The frozen-temperature approximation by itself does not justify this extra reduction.

After onset, protrusions reach more weakly saline liquid and advance faster, while grooves accumulate rejected brine. The planar interface develops cells and, as growth becomes sufficiently strong, crystal dendrites with concentrated liquid between them. Nonlinear competition changes the selected spacing; linear rates alone cannot fix the final geometry. The interdendritic liquid forms a mushy layer, concentrates toward the eutectic composition, and ultimately freezes into a salt-bearing eutectic product when it reaches $T_E$. This replaces the pure planar salt-rejection picture with trapping and freezing of brine between crystals.

Use a planar saline Stefan problem with upward coordinate $z$, the initial contact at $z=0$, and phase boundaries $z=a(t)$ and $z=b(t)$ enclosing pure ice, where $a<b$. Fresh liquid occupies $z>b$ and brine occupies $z<a$. We assume negligible bulk flow, equal constant mass density $\rho$, specific heat capacity $c_p$ and thermal diffusivity $\kappa$ in all regions, and zero salt content and salt transport in the ice. Equal densities remove phase-change volume flow; suppressing convection isolates the molecular-transport mechanism. Different material properties would change the numerical coefficients. Set $K=\rho c_p\kappa$ for the common thermal conductivity and $\Delta T=T_m-T_{\infty }>0$. Denote the brine salt diffusion coefficient by $D$.

Use a linear ice liquidus, $T_L(C)=T_m-mC$, with $m>0$ and $C$ the salt mass fraction. Assume the initial brine is a stable liquid, $T_{\infty }>T_L(C_0)$, and all concentrations considered are below the eutectic composition. Thus $R=m{C}_0/\Delta T>1$. These assumptions exclude independent nucleation in a supercooled brine or an eutectic system event, neither of which is specified by the initial data alone. Start with a negligible seed of ice and use local phase equilibrium without interfacial kinetics or curvature. Temperature differences may be in Celsius, since only differences enter this calculation.

WriteThe paper calls $S$ a Stefan number; it is the latent-to-sensible heat ratio, reciprocal to another common Stefan number convention. At the lower phase boundary, define $T_i=T_L(C_i)$ and letThe liquidus relation is $\vartheta =Rc$.

A similarity solution gives an explicit calculation of the two positions. Putand use $u=z/(2\sqrt{\kappa t})$, $v=z/(2\sqrt{Dt})$. The temperatures and salinities areThese error function and complementary error function profiles satisfy the heat equation and the salt diffusion equation, their far-field conditions, and the interfacial temperature conditions. The fresh-water temperature is constant because the interface and the far field are both at $T_m$.

Salt conservation at the moving lower phase boundary requiresFor upward motion this is dilution by melting salt-free ice, rather than salt rejection by freezing brine. Substitution gives the dilution function for a melting saline Stefan front:For $A>0$, $0<c<1$, so the interfacial brine is fresher than the remote liquid.

The Stefan condition at the upper boundary is $\rho L\dot{b}=K{T}_{s,z}(b)$, since the fresh liquid has no temperature gradient. At the lower boundary it isThese signs follow from the jump in enthalpy: the upper front freezes liquid while a positive $\dot{a}$ melts solid. With $E=\mathrm{erf}B-\mathrm{erf}\delta$, they reduce toTogether with $\delta =ϵA$, these equations determine $A,B,\vartheta$, and hence both positions, without discarding the salt-diffusion correction.

For the stated large latent-to-sensible heat ratio, the layer is thin relative to the thermal diffusion length. Expanding the thermal equations for $B,\delta \ll 1$ givesConsequently a useful leading calculation iswhere the positive $A$ is obtained fromThe left side decreases with $A\ge 0$ while the right side increases, and their values at zero and infinity guarantee a unique positive root for large $S$. Thus this leading calculation includes the translation of the lower boundary as well as the increasing thickness.

If the scale separation also obeys $ϵSA\ll 1$, the familiar simpler result iswithThis last simplification needs the logarithmic refinement $ϵS\sqrt{\log (RS)}\ll 1$. The algebraic ordering $ϵ\ll S^{-1}$ alone should not be used to discard an arbitrarily large logarithmic correction; the preceding coupled equations remain the appropriate calculation when that refinement is unavailable. This distinction is captured by large latent heat in a freezing and melting ice layer.

The illustration uses $S=40$, $ϵ=2.5\times 10^{-4}$ and $R=2$. Solving the full equations gives $A=1.73707$, $B=0.0143053$ and $\vartheta =0.0158766$. It shows the ice layer between freshwater and cold brine, with both fronts advancing upward and a strongly diluted lower liquid boundary.

The phase diagram shows the spatial path from remote brine to the lower interface: temperature first changes over $\sqrt{\kappa t}$ at almost unchanged salinity, then salinity changes over its much smaller diffusion scale at nearly constant temperature. The liquid path ends on the liquidus at $(C_i,T_i)$; the solid has $C=0$ and its temperature rises from $T_i$ to $T_m$. The eutectic position is schematic, with $C_E=2C_0$ in the illustration, and is not used in the calculation. A point initially in the fresh layer freezes when $b$ reaches it, cools in the ice, and later melts when $a$ reaches it. The inset indicates this temporal path in the opposite direction through the solid branch and into the liquid.

The mechanism is simultaneous upper freezing and lower melting, with net growth of the ice thickness. Cold brine accepts most of the latent heat released by upper freezing. Salt reaching the lower contact lowers its equilibrium melting temperature, and melting freshens that liquid until its liquidus is close to $T_m$. The heat delivered through the ice supplies the much smaller melting demand there. The remote brine remains liquid even though it is below the pure-water melting temperature, because it lies above its own saline liquidus. Thus “cold” does not by itself decide which phase is stable. These conclusions apply while the layers remain effectively deep and the stated no-convection, pure-ice and phase-equilibrium assumptions hold.

Take $z$ positive downwards from the roof. Write $T_0=T_m-m{C}_0$, $C_B=(T_m-T_B)/m$, $\Delta T=T_0-T_B=m(C_B-C_0)>0$ and $\Delta C=C_B-C_0$. The cooled magma follows the decreasing liquidus from $(C_0,T_0)$ towards $(C_B,T_B)$; the initially superheated liquid starts at $(C_0,T_{\infty })$ above that liquidus. The solid has zero solute concentration. At each temperature in the mushy layer, a horizontal tie line joins the pure solid to the residual liquid on the liquidus. The lever rule gives the liquid fraction from the bulk concentration. Since $T_B>T_E$, this path stops before the eutectic temperature and does not cross the eutectic composition.

The porosity $\varphi$ denotes the liquid fraction, so $1-\varphi$ is the solid fraction. Equal phase mass densities remove volume-change flow; the stable density stratification suppresses convection. In the stagnant mushy-layer model, define bulk specific enthalpy and bulk solute concentration byThe arbitrary reference of specific enthalpy has been omitted. The two conservation laws in $0<z<h(t)$ areHere $\kappa =k_T/(\rho c_p)$ is the thermal diffusivity, with $k_T$ the thermal conductivity. The positive $L{\varphi }_t$ term records increased specific enthalpy on melting; during freezing it supplies latent heat. In the liquid $z>h(t)$, the heat equation and solute diffusion equation arewhere $D$ is the solutal diffusivity. Neglecting solute diffusion inside the mushy layer does not permit dropping $D{C}_{zz}$ in the liquid at this stage.

Use $T(0,t)=T_B$, liquid $T\to T_{\infty }$ and $C\to C_0$ as $z\to \infty$, and initially $h=0$, $T=T_{\infty }$, $C=C_0$ for $z>0$. These are the half-space boundary conditions appropriate before cooling reaches the bottom of the chamber. For a closed chamber of finite depth $H$, replace the far-field conditions by the specified bottom conditions, for example $T_z=C_z=0$ at an insulated impermeable floor; the half-space similarity solution then ceases to apply when the thermal penetration depth approaches $H$.

At $z=h(t)$, let $C_i$ and $T_i=T_m-m{C}_i$ be the common liquid concentration and temperature, and let ${\varphi }_i$ be the limiting porosity on the mush side. Continuity of $T,C$, the Rankine-Hugoniot condition for solute, and the interfacial conservation of energy giveThe first condition has the sign of solute rejection into the liquid. For the sharp-edge stagnant mushy-layer model with nonzero liquid solutal diffusivity, close the free-boundary problem by marginal equilibrium at a mush-liquid boundary:This prevents constitutional supercooling immediately ahead of the mushy layer. A small solid fraction jump at its edge is allowed: imposing ${\varphi }_i=1$ as well as these finite-$D$ conditions would generally overdetermine the reduced model. At the roof, $C=C_B$ follows from the liquidus, and no additional solute-flux boundary condition is needed in the diffusion-free mush.

To obtain the large-concentration similarity solution, putThe positive superheat specifies the physically intended liquid initial state. On a similarity solution, $C_i,{\varphi }_i$ are constant, so every newly incorporated level leaves the same constant $B={\varphi }_i{C}_i$. Write $C_i=C_0+\Delta C\delta$ and $B=\Delta C(\mathcal{C}+a)$. Then throughout the mushy layerFor $a,\theta =O(1)$, $\mathcal{C}\gg 1$, and $\mathcal{S}/\mathcal{C}=O(1)$, the effective heat capacity is constant to relative error $O({\mathcal{C}}^{-1})$. Thus setIntegration of the similarity solution ordinary differential equation gives the leading analytical profilesThe temperature is $T=T_0+\Delta T\theta$. In the mushy layer, the concentration and porosity are the displayed $C,\varphi$; in the liquid,These retain the liquid solutal boundary layer. For completeness, finite-$r$ values of $\delta ,a,\lambda$ are determined analytically, to the same large-$\mathcal{C}$ order, by settingand solvingThe solute jump gives ${\varphi }_i=1-b/(\mathcal{C}+\delta )$ exactly; replacing $\mathcal{C}$ by $\mathcal{C}+\delta$ on the right of the last equation retains that jump's next-order factor, but does not make the linearized thermal profiles exact at finite $\mathcal{C}$. The branch has $0\le \delta <1$, $0<\varphi \le 1$. All these profiles are leading asymptotic expressions, not exact solutions of the nonlinear finite-$\mathcal{C}$ heat equation.

For $r\to 0$ at fixed positive $\lambda$, the complementary error function asymptotic gives $K(\lambda /\sqrt{r})\sim \sqrt{\pi }\lambda /\sqrt{r}$, hence $\delta =O(r)$, $b=O(r)$, $a\to 0$, and ${\varphi }_i\to 1$. The result simplifies toIn particular, $\varphi (0,t)=C_0/C_B=\mathcal{C}/(\mathcal{C}+1)$ and $\varphi (h^{-},t)=1$. There is no finite interfacial latent heat jump in this limit: the latent heat is released continuously throughout the mushy layer. Matching the two temperature gradients givesThe printed final equation is missing the square on $\Omega$ in the exponential. The corrected exponent follows directly from differentiating $\mathrm{erf}(\Omega \eta )$ and is consistent with ${\Omega }^2=1+\mathcal{S}/\mathcal{C}$. The positive root is unique: the mush-side gradient decreases from infinity to zero with $\lambda$, whereas ${\theta }_{\infty }K(\lambda )$ increases. The zero-superheat limit is singular and is not described by a finite positive $\lambda$ in this two-region construction.