Darken's equations

In 1948, Lawrence Stamper Darken published an article entitled "Diffusion, Mobility and Their Interrelation through Free Energy in Binary Metallic Systems", in which he derived two equations describing solid-state diffusion in binary solutions. Specifically, the equations Darken created relate “binary chemical diffusion coefficient to the intrinsic and self diffusion coefficients”.[1] The equations apply to cases when a solid solution's two interdiffusing components do not have the same coefficient of diffusion. The result of this article had a large impact on the understanding of solid state diffusion and as a result the equations have come to be known as “Darken’s equations”.

Darken's first equation is

${\displaystyle \nu =(D_{1}-D_{2}){\frac {\partial N_{1}}{\partial x}}=(D_{2}-D_{1}){\frac {\partial N_{2}}{\partial x}}.}$

Darken's first equation is used to calculate marker velocity, given here as ${\displaystyle \nu }$, in respect to a binary system where the different components have their own corresponding diffusion coefficients, D₁ and D₂, as was discussed in the Kirkendall experiment.[2] The marker velocity is in terms of length per unit time and the diffusion coefficients are in terms of length squared per unit time. The variables N₁ and N₂ represent the atom fraction of the corresponding component. In addition, the variable x is the distance term. It is important to note that this equation only holds in situations where the total concentration remains constant.

For a binary system this is defined by C₁ + C₂ = C, where C is the overall concentration of the system that remains constant, and C₁ and C₂ are the corresponding component's concentration. This is equivalent to saying that the partial molar volumes of the two components are constant and equal.[3] In addition, the ends of the system need to be fixed in position for the equation to hold. These constraints will be further analyzed in the derivation.

Darken's second equation is

${\displaystyle {\tilde {D}}=(N_{1}D_{2}+N_{2}D_{1}){\frac {\partial \ln a_{1}}{\partial \ln N_{1}}}.}$

Darken's second equation is used to calculate the chemical diffusion coefficient (also known as the inter-diffusion coefficient), ${\displaystyle {\tilde {D}}}$, for a binary solution.[2] The variables N and D are the same as previously stated for Darken's first equation. In addition, the variable a₁ is the activity coefficient for the component one. Similar to the first equation, this equation only holds in situations when the total concentration remains constant.

To derive these equations Darken mainly references Kirkendall and Smigelskas’s experiment,[4] and W. A. Johnson’s experiment, along with other findings within the metallurgical community.

Experimental methods

In deriving the first equation, Darken referenced Simgelskas and Kirkendall's experiment, which tested the mechanisms and rates of diffusion and gave rise to the concept now known as the Kirkendall effect. For the experiment, inert molybdenum wires were placed at the interface between copper and brass components, and the motion of the markers was monitored. The experiment supported the concept that a concentration gradient in a binary alloy would result in the different components having different velocities in the solid solution. The experiment showed that in brass zinc had a faster relative velocity than copper, since the molybdenum wires moved farther into the brass. In establishing the coordinate axes to evaluate the derivation, Darken refers back to Smigelskas and Kirkendall’s experiment which the inert wires were designated as the origin.[2]

In respect to the derivation of the second equation, Darken referenced W. A. Johnson’s experiment on a gold–silver system, which was performed to determine the chemical diffusivity. In this experiment radioactive gold and silver isotopes were used to measure the diffusivity of gold and silver, because it was assumed that the radioactive isotopes have relatively the same mobility as the non-radioactive elements. If the gold–silver solution is assumed to behave ideally, it would be expected the diffusivities would also be equivalent. Therefore, the overall diffusion coefficient of the system would be the average of each components diffusivity; however, this was found not to be true.[2] This finding led Darken to analyze Johnson's experiment and derive the equation for chemical diffusivity of binary solutions.

Darken's first equation

Background

As stated previously, Darken's first equation allows the calculation of the marker velocity ${\displaystyle \nu }$ in respect to a binary system where the two components have different diffusion coefficients. For this equation to be applicable, the analyzed system must have a constant concentration and can be modeled by the Boltzmann–Matano solution.

For the derivation, a hypothetical case is considered where two homogeneous binary alloy rods of two different compositions are in contact. The sides are protected, so that all of the diffusion occurs parallel to the length of the rod. In establishing the coordinate axes to evaluate the derivation, Darken sets the x-axis to be fixed at the far ends of the rods, and the origin at the initial position of the interface between the two rods. In addition this choice of a coordinate system allows the derivation to be simplified, whereas Smigelskas and Kirkendall's coordinate system was considered to be the non-optimal choice for this particular calculation as can be seen in the following section. At the initial planar interface between the rods, it is considered that there are infinitely small inert markers placed in a plane which is perpendicular to the length of the rods. Here, inert markers are defined to be a group of particles that are of a different elemental make-up from either of the diffusing components and move in the same fashion. For this derivation, the inert markers are assumed to be following the motion of the crystal lattice. The motion relative to the marker is associated with diffusion, ${\displaystyle -D_{1}{\tfrac {\partial C_{1}}{\partial y}}}$, while the motion of the markers is associated with advection, ${\displaystyle C_{1}\nu }$. Fick’s first law, the previous equation stated for diffusion, describes the entirety of the system for only small distances from the origin, since at large distances advection needs to be accounted for. This results in the total rate of transport for the system being influenced by both factors, diffusion and advection.[2]

Derivation

The derivation starts with Fick's first law using a uniform distance axis y as the coordinate system and having the origin fixed to the location of the markers. It is assumed that the markers move relative to the diffusion of one component and into one of the two initial rods, as was chosen in Kirkendall's experiment. In the following equation, which represents Fick's first law for one of the two components, D₁ is the diffusion coefficient of component one, and C₁ is the concentration of component one:

${\displaystyle -D_{1}{\frac {\partial C_{1}}{\partial y}}.}$

This coordinate system only works for short range from the origin because of the assumption that marker movement is indicative of diffusion alone, which is not true for long distances from the origin as stated before. The coordinate system is transformed using a Galilean transformation, y = x − νt, where x is the new coordinate system that is fixed to the ends of the two rods, ν is the marker velocity measured with respect to the x axis. The variable t, time, is assumed to be constant, so that the partial derivative of C₁ with respect to y is equal to the partial of C₁ with respect to x. This transformation then yields

${\displaystyle -D_{1}{\frac {\partial C_{1}}{\partial x}}.}$

The above equation, in terms of the variable x, only takes into account diffusion, so the term for the motion of the markers must also be included, since the frame of reference is no longer moving with the marker particles. In the equation below, ${\displaystyle \nu }$ is the velocity of the markers.

${\displaystyle -\left[D_{1}{\frac {\partial C_{1}}{\partial x}}-C_{1}\nu \right].}$

Taking the above equation and then equating it to the accumulation rate in a volume results in the following equation. This result is similar to Fick's second law, but with an additional advection term:

${\displaystyle {\frac {\partial C_{1}}{\partial t}}={\frac {\partial }{\partial x}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}-C_{1}\nu \right].}$

The same equation can be written for the other component, designated as component two:

${\displaystyle {\frac {\partial C_{2}}{\partial t}}={\frac {\partial }{\partial x}}\left[D_{2}{\frac {\partial C_{2}}{\partial x}}-C_{2}\nu \right].}$

Using the assumption that C, the total concentration, is constant, C₁ and C₂ can be related in the following expression:

${\displaystyle C=C_{1}+C_{2}.}$

The above equation can then be used to combine the expressions for ${\displaystyle {\tfrac {\partial C_{1}}{\partial t}}}$ and ${\displaystyle {\tfrac {\partial C_{2}}{\partial t}}}$ to yield

${\displaystyle {\frac {\partial C}{\partial t}}={\frac {\partial }{\partial x}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}-C\nu \right].}$

Since C is constant, the above equation can be written as

${\displaystyle 0={\frac {\partial }{\partial x}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}-C\nu \right].}$

The above equation states that ${\displaystyle \textstyle D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}-C\nu }$ is constant because the derivative of a constant is equal to zero. Therefore, by integrating the above equation it is transforms to ${\displaystyle \textstyle D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}-C\nu =I}$, where ${\displaystyle I}$ is an integration constant.

At relative infinite distances from the initial interface, the concentration gradients of each of the components and the marker velocity can be assumed to be equal to zero. Based on this condition and the choice for the coordinate axis, where the x axis fixed at the far ends of the rods, I is equal zero.[5] These conditions then allow the equation to be rearranged to give

${\displaystyle \nu ={\frac {1}{C}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}\right].}$

Since C is assumed to be constant, ${\displaystyle \textstyle {\frac {\partial C_{1}}{\partial x}}=-{\frac {\partial C_{2}}{\partial x}}}$. Rewriting this equation in terms of atom fraction ${\displaystyle N_{1}={\tfrac {C_{1}}{C}}}$ and ${\displaystyle N_{2}={\tfrac {C_{2}}{C}}}$ yields[2]

${\displaystyle \nu =(D_{1}-D_{2}){\frac {\partial N_{1}}{\partial x}}=(D_{2}-D_{1}){\frac {\partial N_{2}}{\partial x}}.}$

Accompanying derivation

Referring back to the derivation for Darken's first equation, ${\displaystyle \nu }$ is written as

${\displaystyle \nu ={\frac {1}{C}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}\right].}$

Inserting this value for ${\displaystyle \nu }$ in ${\displaystyle \textstyle {\frac {\partial C}{\partial t}}={\frac {\partial }{\partial x}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}-C_{1}\nu \right]}$ gives

${\displaystyle {\frac {\partial C_{1}}{\partial t}}={\frac {\partial }{\partial x}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}-{\frac {C_{1}}{C}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}+D_{2}{\frac {\partial C_{2}}{\partial x}}\right]\right].}$

As stated before, ${\displaystyle \textstyle {\frac {\partial C_{1}}{\partial x}}=-{\frac {\partial C_{2}}{\partial x}}}$, which gives

${\displaystyle {\frac {\partial C_{1}}{\partial t}}={\frac {\partial }{\partial x}}\left[{\frac {C_{1}+C_{2}}{C}}D_{1}{\frac {\partial C_{1}}{\partial x}}-{\frac {C_{1}}{C}}\left[D_{1}{\frac {\partial C_{1}}{\partial x}}-D_{2}{\frac {\partial C_{1}}{\partial x}}\right]\right].}$

Rewriting this equation in terms of atom fraction ${\displaystyle N_{1}={\tfrac {C_{1}}{C}}}$ and ${\displaystyle N_{2}={\tfrac {C_{2}}{C}}}$ yields

${\displaystyle {\frac {\partial N_{1}}{\partial t}}={\frac {\partial }{\partial x}}\left[(N_{2}D_{1}+N_{1}D_{2}){\frac {\partial N_{1}}{\partial x}}\right].}$

By using ${\displaystyle \lambda \equiv {\tfrac {x}{t^{1/2}}}}$ and solving to the form ${\displaystyle N_{1}=f(\lambda )}$, it is found that

${\displaystyle -{\frac {1}{2}}\lambda \,dN_{1}=d[(N_{2}D_{1}+N_{1}D_{2}){\frac {dN_{1}}{d\lambda }}].}$

Integrating the above gives the final equation:

${\displaystyle D=D_{1}N_{2}+D_{2}N_{1}.}$

This equation is only applicable for binary systems that follow the equations of state and the Gibbs–Duhem equation. This equation, as well as Darken's first law, ${\displaystyle \nu =(D_{2}-D_{1}){\tfrac {\partial N_{2}}{\partial x}}}$, gives a complete description of an ideal binary diffusion system.[2] This derivation was the approach taken by Darken in his original 1948, though shorter methods can be used to attain the same result.

Darken's second equation

Background

Darken's second equation relates the chemical diffusion coefficient, ${\displaystyle {\tilde {D}}}$, of a binary system to the atomic fractions of the two components. Similar to the first equation, this equation is applicable when the system does not undergo a volume change. This equation also only applies to multicomponent systems, including binary systems, that obey the equations of state and the Gibbs–Duhem equations.

Derivation

To derive Darken's second equation the gradient in Gibb's chemical potential is analyzed. The gradient in potential energy, denoted by F₂, is the force which causes atoms to diffuse.[2] To begin, the flux J is equated to the product of the differential of the gradient and the mobility B, which is defined as the diffusing atom's velocity per unit of applied force.[6] In addition, N_A is Avogadro's number, and C₂ is the concentration of diffusing component two. This yields

${\displaystyle J=-{\frac {1}{N_{A}}}{\frac {dF_{2}}{dx}}B_{2}C_{2},}$

which can be equated to the expression for Fick's first law:

${\displaystyle -D_{2}{\frac {dC_{2}}{dx}},}$

so that the expression can be written as

${\displaystyle D_{2}{\frac {dC_{2}}{dx}}={\frac {1}{N_{\text{A}}}}{\frac {dF_{2}}{dx}}B_{2}C_{2}.}$

After some rearrangement of variables the expression can be written for D₂, the diffusivity of component two:

${\displaystyle D_{2}={\frac {dF_{2}}{dC_{2}}}{\frac {B_{2}C_{2}}{N_{\text{A}}}}.}$

Assuming that atomic volume is constant, so C = C₁ + C₂,

${\displaystyle {\frac {1}{N_{\text{A}}}}{\frac {dF_{2}}{dN_{2}}}B_{2}N_{2}.}$

Using a definition activity, ${\displaystyle dF_{2}=RT\,d\ln a_{2}}$, where R is the gas constant, and T is the temperature, to rewrite the equation in terms of activity gives

${\displaystyle D_{2}=kTB_{2}{\frac {d\ln a_{2}}{d\ln N_{2}}}.}$

The above equation can be rewritten in terms of the activity coefficient γ, which is defined in terms of activity by the equation ${\displaystyle \gamma _{2}=a_{2}/N_{2}}$. This yields

${\displaystyle D_{2}=kTB_{2}\left(1+N_{2}{\frac {d\ln \gamma _{2}}{d\ln N_{2}}}\right).}$

The same equation can also be written for the diffusivity of component one, ${\displaystyle D_{1}=kTB_{1}\left(1+N_{1}{\tfrac {d\ln \gamma _{1}}{d\ln N_{1}}}\right)}$, and combining the equations for D₁ and D₂ gives the final equation:[2]

${\displaystyle {\tilde {D}}=(N_{1}D_{2}+N_{2}D_{1}){\frac {\partial \ln a_{1}}{\partial \ln N_{1}}}.}$

Applications

Darken’s equations can be applied to almost any scenario involving the diffusion of two different components that have different diffusion coefficients. This holds true except in situations where there is an accompanying volume change in the material because this violates one of Darken’s critical assumptions that atomic volume is constant. More complicated equations than presented must be used in cases where there is convection. One application in which Darken’s equations play an instrumental role is in analyzing the process of diffusion bonding.[7] Diffusion bonding is used widely in manufacturing to connect two materials without using adhesives or welding techniques. Diffusion bonding works because atoms from both materials diffuse into the other material, resulting in a bond that is formed between the two materials. The diffusion of atoms between the two materials is achieved by placing the materials in contact with each other at high pressure and temperature, while not exceeding the melting temperature of either material. Darken’s equations, particularly Darken’s second equation, come into play when determining the diffusion coefficients for the two materials in the diffusion couple. Knowing the diffusion coefficients is necessary for predicting the flux of atoms between the two materials, which can then be used in numerical models of the diffusion bonding process, as, for example, was looked at in the paper by Orhan, Aksoy, and Eroglu when creating a model to determine the amount of time required to create a diffusion bond.[7] In a similar manner, Darken’s equations were used in a paper by Watanabe et al., on the nickel-aluminum system, to verify the interdiffusion coefficients that were calculated for nickel aluminum alloys.[8]

Application of Darken’s first equation has important implications for analyzing the structural integrity of materials. Darken’s first equation, ${\displaystyle \textstyle v=(D_{2}-D_{1}){\frac {\partial N_{2}}{\partial x}}}$, can be rewritten in terms of vacancy flux, ${\displaystyle \textstyle J_{v}=(D_{2}-D_{1}){\frac {\partial N_{2}}{\partial x}}}$.[9] Use of Darken’s equation in this form has important implications for determining the flux of vacancies into a material undergoing diffusion bonding, which, due to the Kirkendall effect, could lead to porosity in the material and have an adverse effect on its strength. This is particularly important in materials such as aluminum nickel superalloys that are used in jet engines, where the structural integrity of the materials is extremely important. Porosity formation, known as Kirkendall porosity, in these nickel-aluminum superalloys have been observed when diffusion bonding has been used.[10][11] It is important then to use Darken’s findings to predict this porosity formation.

See also

• Gibbs-Duhem equation#Ternary and multicomponent solutions and mixtures ("Lawrence Stamper Darken has shown ...")

References

1. Trimble, L. E., D. Finn, and A. Cosgarea, Jr. "A Mathematical Analysis of Diffusion Coefficients in Binary Systems". Acta Metallurgica 13.5 (1965): 501–507.
2. Darken, L. S. "Diffusion, mobility and their interrelation through free energy in binary metallic systems". Trans. AIME 175.1 (1948): 184–194.
3. Sekerka, R. F. "Similarity Solutions for a Binary Diffusion Couple with Diffusivity and Density Dependent on Composition". Progress in Materials Science 49 (2004): 511–536.
4. Smigelskas, A. D., and E. O. Kirkendall. "Zinc diffusion in alpha brass". Trans. AIME 171 (1947): 130–142.
5. Glicksman, Martin E. Diffusion in Solids: Field theory, Solid-Stat Principles, and Applications. New York: John Wiley and Sons, 2000.
6. Gaskell, David R. An Introduction to: Transport Phenomena in Materials Engineering. 2nd ed. New York; Momentum Press, 2012.
7. Orhan, N , M Aksoy, and M Eroglu. "A new model for diffusion bonding and its application to duplex alloys." Materials Science and Engineering 271.1-2 (1999): 458-468. Science Direct. Web.
8. Watanabe, M., Z. Horita, T. Sano, and M. Nemoto. "Electron microscopy study of Ni/Ni3Al diffusion-couple interface-II. Diffusivity measurement." Acta Metallurgica et Materialia 42.10 (1994): 3389-3396. Science Direct. Web.
9. "DoITPoMS - TLP Library Diffusion - Derivation of darken equation".
10. Karunaratne, M.S.A, P. Carter, and R.C. Reed. "On the diffusion of aluminium and titanium in the Ni-rich Ni–Al–Ti system between 900 and 1200°C." Acta Materialia 49.5 (2001): 861-875. Science Direct. Web.
11. Janssen, M.M.P.. "Diffusion in the nickel-rich part of the Ni−Al system at 1000° to 1300°C; Ni3Al layer growth, diffusion coefficients, and interface concentrations." Metallurgical Transactions 4.6 (1973): 1623-1633.Springer Link. Web.