Solved with COMSOL Multiphysics 5.2 Effective Diffusivity in Porous Materials ‘This example introduces the concept of effective diffusivity in porous media by comparing the transport through an artificial porous structure described in a detailed. model with a simplified homogencous porous media approach using effective transport properties. The exercise consists of two parts, The first part describes how to create the model with a detailed geometry. The second part shows how to define a homogeneous model for porous media using an effective diffusivity calculated using the detailed model from the frst part, Introduction ‘Transport through porous structures is usually treated using simplified homogeneous models with effective transport properties. This is in most cases a necessity, since the typical dimensions of the pores and particles making up the porous structure are several orders of magnitude smaller than the size of the domain that is to be modeled. However, it might be interesting to investigate the assumptions and simplifications done when homogenizing a porous structure by comparing a homogeneous mode! with a model defined using the detailed structure.Solved with COMSOL Muleiphysies 5.2 ‘The artificial porous structure used in this example is shown in Figure 1 below. Concentration boundary indaries ‘02-01 0 03 02 03 04 05 06 O7 cB 09 1 10 Figure 1: Artificial porous structure. The domain colored in ved is accesible for diffusion. Model Definition ‘The model equation in the modeled domain shown in Figuve 1 is the time-dependent equation ae S4V DV.) = 0 where ¢ denotes concentration (mol/m? using SI units) and D the diffusion coeficient (m?/s) of the solute. ‘The boundary conditions are of three different types. A concentration boundary condition applies at the left vertical boundary in Figuse 1, Tes expressed as c= ey where ¢q isa given concentration. ‘The right vertical boundary in Figure 1 is set according to (-DVe)-m = ky (e-e)) where ky, is the mass transfer coefficient (m/s), and ¢y is the concentration in a bulk solution outside of the porous structure. All other boundaries are insulating boundaries according to 2 | EFFECTIVE DIFFUSIVITY IN POROUS MATERIALSSolved with COMSOL Multiphysics 5.2 (DVe)-n = 0 ‘The initial condition is given by a bell-shaped profile along the x-axis with its maximum atx = Oand a corresponding value of ¢ = ¢9 ety) = egexp-ax”) Assume a gaseous solution with a solute content of 8 mol/m? at the concentration, boundary. The diffusion coefficient is set to 110 m?/s ‘The second part of this exercise uses a homogenized 1D model geometry with effective transport properties and an average porosity. The model equation then becomes: ae ely) = 20. DV.) = 0 where € denotes the average porosity and D" the efiective diffusivity, These properties are calculated from the results of the detailed structure; see the next section. At the boundaries, the concentration and fhix conditions described above apply Results and Discussion ‘The simulations are run for f = 0 to 0.1 s, when the simulation reaches steady state Figure 2 below shows the concentration profile alter 0.05 s in the porous structure, 3 | EFFECTIVE OIFFUSIVITY IN POROUS MATERIALSSolved with COMSOL Muleiphysies 5.2 Already at this stage the concentration has almost reached steady state, which is visible by the nearly linear concentration profile across the struct Time=50.ms_ Surface: Concentration moti’) xa" 1 7| 6 5| 4s as 4| 25 2| y os o| Figure 2: Concentration profile in the modeled artificial porous structure at t = 0.05 ‘When modeling porous media, the exact concentration in the pore structure is not the most important issue because the description of the structure is homogenized and not detailed as in Figure 2. The most interesting issue is then the description of the flux. To calculate the average flux, integrate over the flux boundary and divide by its length, Lp, which yields the following expression: le Knees * Pofinlenenes average Figure 3 shows the value of this integral as a fimetion of time. If you let the process reach steady-state, the average flux becomes 8.05110 molm?/s. Considering the almost linear profile across the structure, itis natural to replace the porous structure with a 1D homogenized structure along the x-axis, It is then possible to calculate the llective diffusivity according to the following:Solved with COMSOL Multiphysics 5.2 (Co ~ Cou 1 =N, average where cout is the average concentration (mol/m:) at the flux boundary, and Ly is the length of the geometry along the x-axis. The average concenttation is obtained by integrating according to the expression below: Ly lf as Cout = 7,048 0 This gives an average concentration yy = 1.61-10~* mol/m®, Using Ly = 8:10 the effective diffusivity is: ‘a a pet = 8051-10 x8.0-10 (3-161 - 10" which yields a value for the effective diffusivity of 2.15-10-6 m?/s compared to the “free” diffusivity of 1-10 m?/s. The effective and “free” diffusivities are usually related according to the equation where € is the porosity of the structure and t the tortuosity, which is a measure of the actual length per unit effective length a molecule has to diffuse in a porous structure. To calculate the porosity of the modeled structure, you integrate the value I over the structure and then divide this by the length and width of the structure: c= pe Jade resulting in a value of 0.382. The value of t can then be calculated to 1.78. In addition, the tortuosity is usually expressed as a power of the porosity, resulting in an expression for the effective diffusivity according to pt. pe? If you use the calculated values for porosity and effective diffusivity, the value for p is 1.60. The experiment: catalysts, soils, and other porous structures is usually in the range 1.5-2 values for p for porous structures used for transport in 5 | EFFECTIVE OIFFUSIVITY IN POROUS MATERIALSSolved with COMSOL Multiphysies 5.2 Using the value ofthe efizctivediasvity, a simple homogenized 1D model provides the possibilty to compare the value of the ux using 2 homogenized model to the valuc using the detailed 2D structure. Figuse 3 shows that thet isan excellent agreement between the model using a detailed geometry and the homogenized model The difference inthe time-dependent fuxis hardly visible between the two cases the evaph 007s o.oo oo 106 0.0055 E 0.005 2 o,004s| 3 0.004] $oooss § 0.003 = aro02s| Figure 3: Average flu at the flux boundary in the detasled 2D model (solid blue line) and the ID homogenized approximation (dashed green line). Notes About the "OMSOL Implementation Both models described above are straightforward to define in COMSOL Multiphysics. (One feature that is of great use in this example is the ability to define integration, coupling operators to generate the values of the integrals needed to evaluate the results. The definition of these integrals is described in detail in the step-by-step instructions below. Application Library path: COuSOL_Multiphysics/Ditfusion/ offective_diffusivity 6 | EFFECTIVE DIFFUSIVITY IN POROUS MATERIALSSolved with COMSOL Multiphysics 5.2 Modeling Instructions From the File menu, choose New. NEW 1 In the New window, click Model Wizard. MODEL WIZARD 1 In the Model Wiz: ‘window, click 20. 2 In the Select physies tree, sclect Chemical Species Transport>Transport of Diluted Species (tds) (Click Add, (Click Study, In the Select study trec, select Preset Studies>Time Dependent, Click Done, GEOMETRY | Import | (imp!) 1 On the Home toolbar, click Import. In the Settings window for Import, locate the Impert section, 2 3 From the Source list, choose COMSOL Multiphysics file 4 Click Browse 5 Browse to the application's Application Library folder and double-click the file effective_diftusivitymphbin 6 Click Import. GLOBAL DEFINITIONS Parameters 1 On the Home toolbar, click Parameters. 2 In the Settings window for Parameters, locate the Parameters section 7 | EFFECTIVE DIFFUSIVITY IN POROUS MATERIALSSolved with COMSOL Multiphysics 5.2 3 In the table, enter the following settings: Name Expression Value Description 2 te-5[m°2/s] TES mils Diffusion coefficient c_max {mol im"3] 3 molim* Peak initial concentration kt sim/s] Simis Mass transfer coefficient a 1000 tooo Dimensionless constant Variables 1 1 On the Home toolbat, click Variables and choose Global Variables. 2 In the Settings window for Variables, locate the Variables section, 3 In the table, enter the following settings: Name Expression Unie Description 0 c_max*exp(a*(-(x/ olin? ‘Initial concentration 0-4{mm] )"2)) DEFINITIONS Next, define selections that will be useful when defining the boundary conditions and. an integration coupling operator, and also during postprocessing, ns toolbar, click Explicit. 2 In the Medel Builder window, right-click Explicit | and choose Rename. 3 In the Rename Explicit dialog box, type Left boundary in the New label text fed. 4 Click 0K. 5 In the Settings window for Explicit, locate the Input Entities section 6 From the Geometrie entity level list, choose B 7 Select Boundary 1 only. inday. Ex icit 2 1 On the Definitions toolbar, click Explicit. 2 In the Medel Builder window, right-click Explicit 2 and choose Rename. 3 In the Rename Expl 4 Click 0K. dialog box, type Right boundary in the New label text field.Solved with COMSOL Multiphysics 5.2 5 In the Settings window for Explicit, locate the Input Entities section. 6 From the Geometric entity level list, choose Boundary. 7 Select Boundary 276 only Explicit 3 1 On the Definitions toolbar, click Explicit. 2 In the Model Builder window, right-click Explicit 3 and choose Rename. 3 In the Rename Explicit dialog box, type Top-right vertex in the New label text field. Click OK, 4 5 In the Settings window for & From the Geome 7 Select Point 532 only. TRANSPORT OF DILUTED SPECIES (TDS) | In the Settings window for ‘Transport of Diluted Species, locate the Transport Mechanisms section, 2 Clear the Conveetion check box, ‘This setting gives a pure diffusion interface. 1 Tach Mode Butera xp che Taser ef ited Spe (a) aoe, hen 2 Inthe Sens window for Transport Tropes, loa the Btn section 3 Inthe De tent fd yp 02 Init 1 In the Model Builder window, under Component | (compl)>Transport of Diluted Species (tds) click Initial Values 1 2 In the Settings window for Initial Values, locate the Initial Values section. 3 In thee text field, type ¢0. Concentration | 1 On the Physies toolbar, click Boundaries and choose Concentration. 2 In the Settings window for Concentration, locate the Boundary Seleetion section. 3. From the Selection list, choose Left boundary. 9 | EFFECTIVE OIFFUSIVITY IN POROUS MATERIALSlo | Solved with COMSOL Muleiphysies 5.2 4 Locate the Concentra n section, Select the Species ¢ check box. 5 In the egg text field, type ¢_max 1 On the Physies toolbar, click Boundaries and choose Fux. 2 In the Settings window for Flux, locate the Boundary Selection section. 3. From the Selection lst, choose Right boundary. 4 Locate the Inward Flux section, From the Flux type list, choose External forced convection 5 Select the Species ¢ check box. 6 In the A text field, type Kf DEFINITIONS Proceed to define a variable for the average flux through the porous structure. Begin by defining an Average coupling operator on the rightmost boundary. Average | (aveop | 1 On the Definitions toolbar, click Component Couplings and choose Average. 2 In the Settings window for Average, locate the Source Selection section, 3 From the Geometrie entity level list, choose Boundary, 4. From the Selection list, choose Right boundary. Variables 2 1 On the Definitions toolbar, click Local Variables 2 In the Settings window for Variables, locate the Variables section. 3 In the table, enter the following settings: Name Expression Unit Description flux_avg__aveopt (k_f*c) mol/(ms) Average flux MeSH In the Model Builder window, under Component | (compl) right-click Mesh | and chooseSolved with COMSOL Multiphysics 5.2 sTupY | Step I: Time Dependent | In the Model Builder window, expand the Study I node, then click Step 1: Time Dependent, 2 In the Settings window for Time Dependent, locate the Study Settings section. 3 From the Time unit list, choose ms 4 In the Times text field, type range (0,2, 100) 5. On the Home toolbar, click Compute. RESULTS Concentration (tds) 1 Click the Zoom Extents button on the Graphies toolbar, ‘The defauls plot shows concentration at the end time, that is, 0.1 seconds. 1 You can plot the concentration at different time steps 2 In the Model Builder window, click Concentration (td), 3 In the Settings window for 2D Plot Group, locate the Data section. 4. From the Time (ms) list, choose 50. 5 On the Coneentration (tds) toolbar, click Plot. ‘Compare this plot to the one shown in Figure 2,RI 2 3 Solved with COMSOL Mulephysies 5.2 Now, plot the average Hux. ID Plot Group 2 ‘On the Home toolbar, click Add Plot Group and choose 1D Plot Group Point Graph | ‘On the ID Plot Group 2 toolbar, click i 1 Graph ID Plot Group 2 1 In the Settings window for Point Graph, locate the Seleetian section, From the Selection list, choose Top-right vertex. (Click Replace Expression in the upper-right comer of the y-axis data section. From the menu, choose Com bles>flux_avg - Average flux 4 In the Model Builder window, click 1D Plot Group 2. 5. In the Settings window for 1D Plot Group, click to expand the Title section, 6 In the Label text field, type Molar fluxes. 7 Locate the Title section. From the Title type list, choose None. 8 Locate the Plot Settings section. Select the y-axis label check box 9 In the associated text field, type Average flux (mol/(n*s)) ¥0 On the Molar fluxes toolbat, click Plot. 0.008 = 0.06 ° 20 30 300 0 wo ‘Time (ms) To get the porosity of the domain for the 1D model, perform a surface integration.Solved with COMSOL Multiphysics 5.2 Surface Integration ‘On the Results toolbar, click Mare Derived Values and choose Integrat Integrat Derived Values I In the Settings window for Surface Integration, locate the Selection section. 2. From the Seleetion list, choose All domains, 3 Locate the Expression section. In the Expression text field, rype 1/(0-8{mn] )~2. ‘The denominator in this expression represents the product of the lengch and the Width of the 2D model structure 4 Click the Evaluate button, TABLE 1 Go to the Table window. ‘The evaluated value of the integral should be close to 0.383. RooT Now turn to the 1D model. 1 In the Model Builder window, click the root node. 2. On the Home toolbar, click Add Component and choose ID, Abb PHYsics 1 On the Home toolbar, click Add Physies to open the Add Physies window. 2 Go to the Add Physies window. 3 Inthe Add physies tree, select Chemical Species Transport>Transport of Diluted Species (tas). 4 Find the Physies interfaces in study subsection. In the table, enter the following settings Studies Solve Study 5 Click Add to Component in the window toolbar. 6 On the Home toolbar, click Add Physies to close the Add Physics ADD sTUDY 1 On the Home toolbar, click Add Study to open the Add Study window. 3. | EFFECTIVE DIFFUSIVITY IN POROUS MATERIALS| Solved with COMSOL Multiphysics 5.2 2 Go to the Add Study window. 3. Find the Physies interfaces in study subsection. In the table, enter the following settings ysics Solve ‘Transport of Diluted Species (cds) 4 Find the Studies subsection, In the Select study tree, select Preset Studies> Dependent. 5 Click Add Study in the window toolbar 6 On the Home toolbar, click Add Study to close the Add Study window. GEOMETRY 2 Interval | 1 On the Geometry toolbar, click Interval 2 In the Settings window for Interval, locate the Interval section. 3 In the Right endpoint text field, type 86-4. 4 Right-click interval I (il) and choose Build Selected 5 Click the om Extents button on the Graphies toolbar. GLOBAL DEFINITIONS Parameters ‘Add the following parameters to those you already defined, 1 In the Model Builder window, under Global Defi ns click Parameters 2 In the Settings window for Parameters, locate the Parameters section. 3 In the table, enter the following settings: Name Value Description epsilon 0.383 0383 Porosity by 2.180-6[m°2/s] 2.15E-6ms Diffusion coefficient, 10 TRANSPORT OF DILUTED SPECIES 2 (TDS2) ‘On the Physies coolbar, click Transport of Diluted Species (tds) and choose Transport of Diluted Species 2 (tds2)Solved with COMSOL Multiphysics 5.2 1 In the Model Builder window, under Component 2 (comp2) click Transport of Diluted Species 2 (tds2), 2 In the Settings window for Transport of Diluted Species, locate the Transport Mechanisms section 3 Clear the Convection check box, Transport Properties 1 | In the Medel Builder window, expand the Transport of Diluted Species 2 (tds2) node, then click Transport Properties | 2 In the Settings window for Transport Properties, locate the Diffusion section. 3 In the Deg text field, type D1 /epsilon. Initial Values 1 1 In the Model Builder window, under Component 2 (comp2)>Transport of Diluted Species 2 (tds2) click In Values 1 2 In the Settings window for Initial Values, locate the Initial Values section. 3 In the c2 text field, type 60 Concentration | 1 On the Physies toolbar, click Boundaries and choose Concentration Select Boundary 1 only. In the Settings window for Concentration, locate the Concentration section, Select the Species «2 check box In the ¢p..9 text field, type ¢_max toolbar, lick Boundaries and choose Flux. Select Boundary 2 only. In the Settings window for Flux, locate the Inward Flux section, From the Flux type list, choose External forced convection, Select the Species «2 check box. 2 3 4 5 ‘ DEFINITIONS Create a vatiable for the flux in the homogenized 1D model, In the kgca text field, type k_t /epsilon IS | EFFECTIVE DIFFUSIVITY IN POROUS MATERIALS6 | Solved with COMSOL Multiphysics 5.2 Variables 3 1 On the Home toolbar, click Variables and choose Local V2 2 In the Settings window for Variables, locate the Var 3 In the table, enter the following settings: Name Expres Unie Description flux_hom —k_f¥c2 moli(m?'s) Flux, 1D model, MESH 2 1 In the Model Builder window, under Component 2 (comp2) click Mesh 2 2 In the Settings window for Mesh, locate the Mesh Settings section. 3 From the Element size list, choose Extra fine. 4 Click the Build All button, STUDY 2 Step I: Time Dependent 1 In the Model Builder window, expand the Study 2 node, then click Step I: Time Dependent. 2 In the Settings window for Time Dependent, locate the Study Settings section. 3 From the Time unit list, choose ms. 4 In the Times textfield, type range (0,2, 100) 5 On the Home toolbar, click ComputeSolved with COMSOL Multiphysics 5.2 RESULTS Concentration (tds2) ‘The default plot for the ID model shows the concentration for al time steps Line Graph: Concentration mol") moti’) Finally plot the esl forthe ax at he fox boundary inthe homogenized 1D model in the same plot asthe 2D result for comparison Molar fluxes In the Model Builder window, under Results click Molar fluxes. Point Groph 2 (On the Molar fluxes toolbar, click Point Graph, Molar fluxes 1 In the Settings window for Point Graph, locate the Data section. 2 From the Data set list, choose Study 2/Selution 2 (3) (eel2) 3 Select Boundary 2 01 4. Click Replace Expression in the upper-right corner of the y-axis data section. the menu, choose Com 1es>flux_hom - Flux, 1D mode! nent 2>Definitions>Vari 5 Click to expand the Colering and style section. Locate the Coloring and Style section, Find the Line style subsection. From the Line list, choose Dashed. IT | EFFECTIVE DIFFUSIVITY IN POROUS MATERIALSSolved with COMSOL Multiphysics 5.2 6 On the Molar fluxes toolbar, click Plot. ‘Compare the result with that shown in Figure 3